JP5177607B1 - RECEPTION LAYER FORMING RESIN COMPOSITION AND RECEPTION SUBSTRATE, PRINTED MATERIAL, CONDUCTIVE PATTERN AND ELECTRIC CIRCUIT OBTAINED USING THE SAME - Google Patents

Abstract

The problem to be solved by the present invention is that, among the receiving layers capable of carrying a fluid such as ink, a receiving layer having excellent adhesion to various supports can be formed, causing bleeding of the fluid such as ink. It is an object of the present invention to provide a resin composition for forming a receiving layer capable of forming a receiving layer having excellent printability without any problems. The present invention is a resin composition for forming a receiving layer containing a urethane resin (A), a vinyl polymer (B), and an aqueous medium (C), wherein the urethane resin (A) is the urethane resin ( The present invention relates to a resin composition for forming a receiving layer, which has an aliphatic cyclic structure of 2,000 mmol / kg to 5,500 mmol / kg and a hydrophilic group with respect to the total amount of A). is there.
[Selection figure] None

Description

  The present invention relates to a receiving layer forming resin composition capable of receiving a fluid such as ink discharged by various printing methods including an ink jet printing method, a receiving material, and a printed matter such as a conductive pattern.

  In recent years, ink-jet printer-related industries, where growth has been remarkable, have dramatically improved the performance of ink-jet printers and improved ink, making it easy to produce high-definition and clear printability images similar to silver halide photographs. It is becoming possible to obtain. For this reason, ink jet printers are starting to be used not only in homes but also in various fields including the production of large advertising signs.

  On the other hand, the improvement in image quality of inkjet printed materials is largely due to the improvement in printing ink as well as the improvement in performance of the printer. Specific improvements to printing inks include the selection of solvents in the ink and the selection of dyes or pigments. In recent years, pigment inks that are known to have high color development properties comparable to dye inks. Is attracting attention,

  However, even when the pigment ink having the high color developability is used, depending on the composition of the ink receiving layer, a print image having high color density and excellent printability can be formed, such as causing ink bleeding. There were cases where it was difficult. In addition, with the diversification of ink-jet printed materials, various materials are used as a support on which the ink receiving layer is provided. In the conventional ink receiving layer, for example, adhesion to a plastic film such as polyethylene terephthalate is achieved. In this case, the receptor layer may be peeled off with time.

  In addition, the conventionally known printing methods such as the ink jet printing method and the screen printing method are being studied for use in the scene of creating a conductive pattern such as an electronic circuit. This is because with recent demands for higher performance, smaller size, and thinner electronic devices, there is a strong demand for higher density and thinner electronic circuits and integrated circuits.

  As a method for producing a conductive pattern such as the electronic circuit, specifically, a conductive ink containing a conductive material such as silver is printed on the support surface by an ink jet printing method or a screen printing method, and then dried. And the method of heating and light irradiation as needed is mentioned.

  However, even if the conductive ink is directly printed on the surface of various supports, the conductive ink is not easily adhered to the surface of the support, and thus easily peels off. In some cases, disconnection may occur. In particular, the support made of polyimide resin or polyethylene terephthalate resin is flexible, so that it is possible to produce a flexible device that can be bent. However, the support made of polyimide resin or the like is particularly in close contact with ink or resin. Since it is difficult to peel off, it is easy to peel off, which may cause disconnection of the finally obtained electronic circuit or the like, thereby preventing current conduction.

  As a method for solving the above problem, for example, a method of producing a conductive pattern by drawing a pattern by a predetermined method using a conductive ink on an ink receiving substrate provided with a latex layer is known. It is known that an acrylic resin can be used as the latex layer (see Patent Document 1).

  However, the ink receiving layer made of the latex layer constituting the conductive pattern may cause bleeding of the conductive ink, unevenness of the printing thickness, etc. In some cases, it is difficult to form a conductive wire that is generally required to be a thin wire having a width of approximately 0.01 μm to 200 μm.

  Further, when the conductive pattern is formed, a printed matter printed with the conductive ink is generally used for the purpose of bringing the conductive substances contained in the conductive ink into contact with each other to impart conductivity. In many cases, it is heated and baked at a temperature of ℃ or higher.

However, since the ink receiving layer such as the latex layer described in the literature 1 is easily deteriorated due to the influence of heat received in the baking process, the adhesion of the interface between the ink receiving layer and the support is particularly high. It is easy to cause a drop, and even if a very slight force is applied, it may be easily peeled off.
Further, when the baking process is performed, excessive swelling and deformation of the latex layer, which is an ink-receiving layer, are likely to be caused. In addition, since the latex layer often does not have sufficient adhesion to the support before heating in the baking step, the support and the ink receiving layer are not subjected to the baking step. And may cause partial peeling.

  By the way, when forming the conductive pattern, copper is formed on the surface of the conductive pattern from the viewpoint of forming a highly reliable wiring pattern capable of maintaining good electrical conductivity without causing disconnection or the like over a long period of time. In many cases, the plating process is performed by using, for example.

  However, the plating agent used for the plating treatment and the agent used in the cleaning step are usually strongly alkaline and strongly acidic, and thus easily cause peeling from the support such as the receiving layer. In some cases, the conductive pattern may be disconnected.

  Therefore, the conductive pattern is required to have a level of durability that does not cause peeling of the conductive ink-receiving layer from the support even when it is repeatedly immersed in the drug or the like for a long time. ing.

JP 2009-49124 A

  The problem to be solved by the present invention is that, among the receiving layers capable of carrying a fluid such as ink, a receiving layer having excellent adhesion to various supports can be formed, causing bleeding of the fluid such as ink. It is an object of the present invention to provide a resin composition for forming a receiving layer capable of forming a receiving layer having excellent printability without any problems.

  In addition, the second problem to be solved by the present invention is that, among the receiving layers capable of supporting a fluid such as conductive ink, a receiving layer having excellent adhesion to the support can be formed. Even if it is possible to draw fine lines at a level that can be used to achieve higher density of electronic circuits etc. without causing blurring or repellency, and even if chemicals such as plating chemicals or various organic solvents adhere Provided is a resin composition for forming a receiving layer capable of forming a printed matter such as a conductive pattern having a level of durability capable of maintaining good electrical conductivity without causing peeling of the receiving layer from the support. That is.

  As a result of studying the above problems, the present inventors have found that the problems of the present invention can be solved when a specific polyurethane and a vinyl polymer are used in combination.

  That is, the present invention is a resin composition for forming a receiving layer containing a urethane resin (A), a vinyl polymer (B), and an aqueous medium (C), wherein the urethane resin (A) is the urethane resin. The present invention relates to a resin composition for forming a receiving layer, characterized by having an aliphatic cyclic structure of 2,000 mmol / kg to 5,500 mmol / kg and a hydrophilic group with respect to the total amount of resin (A). Is.

  According to the resin composition for forming a receiving layer of the present invention, it has excellent adhesion to various supports, and is excellent in high color printability without causing bleeding of a fluid such as pigment ink. Since it can form a printed image, it can be used, for example, in a recording medium used for manufacturing advertisements, signs, signs, etc. that can be installed indoors and outdoors.

  Further, according to the resin composition for forming a receiving layer of the present invention, a receiving layer having excellent adhesion between the receiving layer and the support can be formed, and high density such as an electronic circuit can be formed without causing bleeding of the conductive ink. For example, a conductive ink containing a conductive substance such as silver can be used because it can provide a thin line with a level capable of drawing a thin line at a level that can be used for the realization of, for example, and can form a receiving layer with excellent durability. Formation of electronic circuits used, formation of organic solar cells, e-book readers, organic EL, organic transistors, flexible printed circuit boards, RFID and other layers that constitute non-contact IC cards, etc., wiring for electromagnetic shielding of plasma displays In general, it can be used in new fields such as the field of printed electronics, such as the manufacture of integrated circuits and organic transistors.

  In addition, the receptor layer formed using the resin composition for forming a receptor layer of the present invention is printed on the receptor substrate of the present invention using a fluid such as conductive ink or plating nucleating agent, and then heated. By forming a cross-linked structure in the ink receiving layer, it is possible to obtain a printed matter (plating structure) having a higher level of durability. Specifically, it is possible to obtain a printed matter (plating structure) having a level of durability that can prevent the conductive material contained in the fluid from being lost from the surface of the receiving layer in the plating process. It becomes.

The resin composition for forming a receiving layer of the present invention is a urethane resin having an aliphatic cyclic structure of 2,000 mmol / kg to 5,500 mmol / kg and a hydrophilic group based on the total amount of the urethane resin (A) ( A), a vinyl polymer (B), an aqueous medium (C), and optionally containing other additives.
The resin composition for forming the receiving layer exclusively absorbs the solvent in the fluid when the fluid containing the conductive material or the pigment comes into contact with the receiving layer that carries the conductive material or the pigment. It can be used for forming.

  The urethane resin (A) and the vinyl polymer (B) contained in the resin composition for forming a receiving layer may be present independently in the aqueous medium (C), and they are composite resin particles. It may exist in a state where (D) is formed.

  Specifically, the composite resin particles (D) refer to those in which part or all of the vinyl polymer (B) is contained in the resin particles formed by the urethane resin (A). At that time, the vinyl polymer (B) may be dispersed in a plurality of particles in the urethane resin (A) particles, and the vinyl polymer (B) as a core layer and a shell layer It is preferable to form core-shell type composite resin particles composed of the urethane resin (A) having a hydrophilic group as In particular, when forming a conductive pattern, it is preferable to use the core-shell type composite resin particles that do not require the use of a surfactant capable of lowering electrical characteristics. In addition, as said composite resin particle (D), it is preferable that the said vinyl polymer (B) is substantially completely covered with the said urethane resin (A), but it is not essential and does not impair the effect of this invention. In a range, a part of the vinyl polymer (B) may be present on the outermost part of the composite resin particle (D).

  Further, as the composite resin particle (D), when the vinyl polymer (B) is more hydrophilic than the urethane resin (A), the vinyl polymer (B) is In the formed resin particles, a part or all of the urethane resin (A) may be present to form composite resin particles.

  Moreover, although the said urethane resin (A) and the said vinyl polymer (B) may form the covalent bond, it is preferable not to form the bond.

  Moreover, it is preferable that the said composite resin particle (D) is an average particle diameter of the range of 5 nm-100 nm from a viewpoint of maintaining favorable water dispersion stability. The average particle diameter here refers to an average particle diameter on a volume basis measured by a dynamic light scattering method, as will be described later in Examples.

  The resin composition for forming a receiving layer of the present invention comprises the urethane resin (A) and the vinyl resin (B), [urethane resin (A) / vinyl resin (B)] = 90/10 to 10/90. It is preferably included in a range, and more preferably in a range of 70/30 to 10/90.

  The resin composition for forming a receiving layer of the present invention does not simply contain the urethane resin (A) and the vinyl monomer (B), and 2,000 mmol as the urethane resin (A). It is important to use a urethane resin having an aliphatic cyclic structure of / kg to 5,500 mmol / kg and a hydrophilic group.

  Here, instead of the urethane resin (A), a receptor layer formed using a urethane resin having an aliphatic cyclic structure content of 1,800 mmol / kg with respect to the urethane resin (A). The resin composition for use may not be able to form a receiving layer excellent in adhesion to various supports. In the resin composition for forming a receiving layer obtained by using a urethane resin having an aliphatic cyclic structure content of 1,800 mmol / kg, a strong alkali or strongly acidic substance is used in the plating process described later. Due to the influence of the plating agent comprising, there may be a case where the durability is remarkably lowered, for example, the receiving layer is peeled off from the support.

  On the other hand, a resin composition for forming a receiving layer obtained by using a urethane resin having an aliphatic cyclic structure content of 6,000 mmol / kg instead of the urethane resin (A), In some cases, it is not possible to form a receiving layer excellent in adhesion of the receiving layer to the support and durability in the plating process.

  Therefore, as the urethane resin (A), it is possible to use a resin having an aliphatic cyclic structure of 3,000 mmol / kg to 5,000 mmol / kg based on the total amount of the urethane resin (A). In particular, it is more preferable for preventing peeling of the receptor layer from the support in the plating process and improving durability.

  Examples of the aliphatic cyclic structure include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a propylcyclohexyl group, a tricyclo [5,2,1,0,2,6] decyl group, and a bicyclo [4]. , 3,0] -nonyl group, tricyclo [5,3,1,1] dodecyl group, propyltricyclo [5,3,1,1] dodecyl group, norbornene group, isobornyl group, dicyclopentanyl group, adamantyl Among them, a cyclohexyl group, a norbornene group, an isobornyl group, and an adamantyl group are preferable for obtaining a printed matter such as a conductive pattern having excellent durability.

  The aliphatic cyclic structure as described above has a polyisocyanate having an aliphatic cyclic structure or an aliphatic cyclic structure as the polyisocyanate (a1) or polyol (a2) used in the production of the urethane resin (A). By using the polyol (a2-2), it can be introduced into the urethane resin (A). Especially, it is preferable to use the urethane resin which has an aliphatic cyclic structure derived from the polyol (a2-2) which has an aliphatic cyclic structure, and polyisocyanate and aliphatic cyclic structure which have an aliphatic cyclic structure are used. It is particularly preferable to use a urethane resin having an aliphatic cyclic structure derived from the polyol (a2-2) that is included in order to greatly improve the adhesion of the receptor layer to various supports. In particular, in the case of the resin composition for forming a receptor layer, the receptor layer from the support can be used even if it is immersed in a plating agent or the like made of a strong alkali or strong acid substance in the plating process described below. Since durability can be improved to the level which does not cause peeling, it is preferable.

  Moreover, as said urethane resin (A), it is necessary to use what has a hydrophilic group from a viewpoint of providing the favorable water dispersion stability in an aqueous medium (C).

  As said hydrophilic group, an anionic group, a cationic group, and a nonionic group can be used, for example, It is more preferable to use an anionic group.

  As the anionic group, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group and the like can be used. Among them, a carboxylate group partially or wholly neutralized with a basic compound or the like It is preferable to use a sulfonate group in order to impart good water dispersibility.

  Examples of basic compounds that can be used for neutralizing the anionic group include organic amines such as ammonia, triethylamine, pyridine, morpholine, alkanolamines such as monoethanolamine, sodium, potassium, lithium, and calcium. A metal base compound is mentioned. When forming a conductive pattern or the like, it is preferable to use the organic amine or alkanolamine because the metal salt compound may inhibit the conductivity.

  When the carboxylate group or sulfonate group is used as the anionic group, they are preferably present in the range of 5 mmol / kg to 4,000 mmol / kg with respect to the entire urethane resin (A), and 50 mmol / kg. It is more preferable to exist in the range of ˜2,000 mmol / kg in order to maintain good water dispersion stability of the urethane resin (A) particles.

Moreover, as said cationic group, a tertiary amino group etc. can be used, for example.
Examples of the acid that can be used when neutralizing part or all of the tertiary amino group include organic acids such as acetic acid, propionic acid, lactic acid, and maleic acid, sulfonic acid, methanesulfonic acid, and the like. Organic sulfonic acids and inorganic acids such as hydrochloric acid, sulfuric acid, orthophosphoric acid and orthophosphorous acid may be used alone or in combination of two or more. In the case of forming a conductive pattern or the like, it is preferable to use acetic acid, propionic acid, lactic acid, maleic acid, or the like because chlorine, sulfur, or the like may inhibit the conductivity.

  Examples of the nonionic group include polyoxyalkylene groups such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a poly (oxyethylene-oxypropylene) group, and a polyoxyethylene-polyoxypropylene group. Can be used. Among these, it is preferable to use a polyoxyalkylene group having an oxyethylene unit in order to further improve the hydrophilicity.

  The urethane resin (A) can be produced by reacting a polyisocyanate (a1), a polyol (a2), and a chain extender as necessary.

  Examples of the polyisocyanate (a1) include aromatic structures such as 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate. Use of polyisocyanates and polyisocyanates containing aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate and aliphatic cyclic structures To do Kill. Among these, it is preferable to use a polyisocyanate having an aliphatic cyclic structure.

  As the polyol (a2) capable of reacting with the polyisocyanate (a1), the polyol (a2-1) having a hydrophilic group is essential, and if necessary, the polyol (a2-2) having an aliphatic cyclic structure, Other polyols (a2-3) can be used in combination.

  Examples of the polyol (a2-1) having a hydrophilic group include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, and 2,2′-dimethylol. Carboxyl group-containing polyols such as valeric acid and polyols having sulfonic acid groups such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid can be used. Examples of the polyol having a hydrophilic group include a polyester polyol having a hydrophilic group obtained by reacting the above-described polyol having a low molecular weight hydrophilic group with various polycarboxylic acids such as adipic acid. It can also be used.

  The hydrophilic group is preferably present in the range of 5 mmol / kg to 4,000 mmol / kg with respect to the total amount of the polyol (a2) used in the production of the urethane resin (A), and is 5 mmol / kg to 2, More preferably, it is used in the range of 000 mmol / kg.

  From the viewpoint of introducing a predetermined amount of an aliphatic cyclic structure into the urethane resin (A), it is preferable to use a polyol (a2-2) having an aliphatic cyclic structure as the polyol (a2).

  Examples of the polyol (a2-2) having an aliphatic cyclic structure include 1,4-cyclohexanedimethanol, cyclobutanediol, cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclooctanediol, and cyclohexanedi. Methanol, tricyclo [5,2,1,0,2,6] decanedimethanol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol, bicyclo [4,3,0] nonanedimethanol, tricyclo [5,3,1,1] dodecanediethanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol, cyclohexanetriol , Hydrogenated bisphenol It can be used 1,3-adamantane diol, a polyol having an aliphatic cyclic structure of relatively low molecular weight. In addition, the molecular weight of the polyol (a2-2) having the aliphatic cyclic structure is based on the formula weight.

  As the polyol (a2-2) having an aliphatic cyclic structure, in addition to those described above, a polyol obtained by reacting a polycarboxylic acid having an aliphatic cyclic structure with an aliphatic polyol may be used. it can.

  Examples of the polycarboxylic acid having an aliphatic cyclic structure include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and these An anhydride or an ester-forming derivative of the compound can be used, and in particular, a polycarboxylic acid having an aliphatic cyclic structure such as 1,2-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid can be used. preferable.

  Examples of the polyol that can be used for the esterification reaction with the polycarboxylic acid having an aliphatic cyclic structure include 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, and 1,2-propylene glycol. 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5 -Hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3- It may be used aliphatic polyols such as propanediol. The aliphatic polyol may be used in combination with an esterification reaction between the polyol (a2-2) having the aliphatic cyclic structure and the polycarboxylic acid.

  As the polyol (a2-2) having an aliphatic cyclic structure, for example, a polycarbonate polyol having an aliphatic cyclic structure can be used. As the polycarbonate polyol having an aliphatic cyclic structure, for example, a polyol obtained by reacting the polyol (a1-1) having a low molecular weight aliphatic cyclic structure with dimethyl carbonate, phosgene or the like is used. be able to.

  As the polycarbonate polyol having an aliphatic cyclic structure, it is preferable to use a polycarbonate polyol having an aliphatic cyclic structure having a number average molecular weight of 800 to 3,000, and a number average molecular weight of 800 to 2,000. It is more preferable to use what has.

  As the polyol (a2-2) having an aliphatic cyclic structure, for example, a polyether polyol having an aliphatic cyclic structure can be used. As the polyether polyol having an aliphatic cyclic structure, for example, the above-described polyol (a1-1) having a low molecular weight aliphatic cyclic structure is used as an initiator, and an alkylene oxide such as ethylene oxide or propylene oxide is added. A polymerized product can be used.

Moreover, as said polyol (a2), other polyol (a2-3) can be used as needed besides the above-mentioned polyol.
As said other polyol (a2-3), polyester polyol other than what was mentioned above, polyether polyol, polycarbonate polyol, etc. can be used, for example.

  Examples of the polyester polyol include ring-opening polymerization of aliphatic polyester polyol and aromatic polyester polyol obtained by esterification reaction of low molecular weight polyol and polycarboxylic acid, and cyclic ester compounds such as ε-caprolactone and γ-butyrolactone. Polyester obtained by reaction, copolymerized polyester thereof, or the like can be used.

  Examples of the low molecular weight polyol that can be used in the production of the polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 3- Methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane and the like can be used alone or in combination of two or more thereof, ethylene glycol, 1,2-propanediol, It is preferable to use 1,3-butanediol or 1,4-butanediol in combination with 3-methyl-1,5-pentanediol, neopentyl glycol, or the like.

  Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and anhydrides or ester-forming derivatives thereof. It is preferable to use an aliphatic polycarboxylic acid such as adipic acid. When the polyester polyol containing the aromatic cyclic structure is used, an aromatic polycarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid, or naphthalenedicarboxylic acid can be used as the polycarboxylic acid. .

  In addition, as the polyether polyol that can be used for the other polyol (a2-3), for example, an alkylene oxide is addition-polymerized using one or more compounds having two or more active hydrogen atoms as an initiator. Things can be used.

  Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, Trimethylolethane, trimethylolpropane and the like can be used.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

  Examples of the polycarbonate polyol that can be used for the other polyol (a2-3) include those obtained by reacting a carbonate with a polyol, and those obtained by reacting phosgene with bisphenol A or the like. Can do.

  As the carbonate ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

  Examples of the polyol capable of reacting with the carbonate ester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3- Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-propa Diol, 2-methyl-1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-methyl-1,8-octanediol, neopentyl glycol, hydroquinone, resorcin, bisphenol-A, bisphenol-F, Relatively low molecular weight dihydroxy compounds such as 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and polyesters such as polyhexamethylene adipate, polyhexamethylene succinate and polycaprolactone Polyols and the like can be used.

  As the polyester polyol, polyether polyol, and polycarbonate polyol, those having a number average molecular weight of 500 to 4,000 are preferably used from the viewpoint of ease of mixing with the matrix resin, and the like. More preferably, 500 is used.

  Examples of the other polyol (a2-3) include, in addition to the polyester polyol, polyether polyol and polycarbonate polyol, for example, ethylene glycol, 1,2-propanediol, 1,3-butanediol, , 4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, di- Hydrophilic group-containing polyols such as methylolpropionic acid, acrylic polyols in which hydroxyl groups are introduced into acrylic copolymers, polybutadiene polyols that are butadiene copolymers containing hydroxyl groups in the molecules, hydrogenated polybutadiene polyols , Ethylene - can be appropriately used partially saponified products of vinyl acetate copolymers.

  Moreover, as a chain extender which can be used when manufacturing the said urethane resin (A), a polyamine, another active hydrogen atom containing compound, etc. can be used.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 3,3′-. Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; Razide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide propionic acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazide methyl-3,5 5-Trimethylcyclohexane can be used, and ethylenediamine is preferably used.

  Examples of the other active hydrogen-containing compound include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and sucrose. , Glycols such as methylene glycol, glycerin, sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone , And water can be used.

  The chain extender is preferably used, for example, in a range where the equivalent ratio of the amino group and excess isocyanate group of the polyamine is 1.9 or less (equivalent ratio), 0.3 to 1.0 (equivalent It is more preferable to use it in the range of the ratio.

  The urethane resin (A) is a conventionally known method, for example, in the absence of a solvent or in the presence of an organic solvent, the polyisocyanate (a1), the polyol (a2), and, if necessary, the chain extender. It can manufacture by making it react.

  The reaction between the polyisocyanate (a1) and the polyol (a2) is in consideration of safety by paying sufficient attention to sudden heat generation and foaming, preferably 50 ° C to 120 ° C, more preferably 80 ° C to 100 ° C. By the reaction temperature, the polyisocyanate (a1) and the polyol (a2) are collectively mixed, or one of them is successively supplied to the other by a method such as dropping, and the reaction is carried out for about 1 hour to 15 hours. It can be carried out.

  The aqueous dispersion of the urethane resin (A) is prepared by reacting the polyisocyanate (a1), the polyol (a2) and, if necessary, a chain extender by the method described above. If necessary, after neutralizing a part or all of the hydrophilic groups such as anionic groups of the urethane resin (A), the urethane resin is mixed with the aqueous medium (C). A urethane resin (A) aqueous dispersion in which (A) is dispersed or partially dissolved in the aqueous medium (C) can be obtained.

  Specifically, by reacting the polyisocyanate (a1) and the polyol (a2) by the method described above, a urethane prepolymer (A ′) having an isocyanate group at the terminal is produced, and if necessary, After neutralizing a part or all of hydrophilic groups such as anionic groups of the urethane prepolymer (A ′), mixing with an aqueous medium (C), and using the chain extender as necessary By extending the chain, a urethane resin (A) aqueous dispersion in which the urethane resin (A) is dispersed or dissolved in the aqueous medium (C) can be obtained.

  The reaction between the polyisocyanate (a1) and the polyol (a2) is, for example, an equivalent ratio of the isocyanate group [X] of the polyisocyanate (a1) and the hydroxyl group [Y] of the polyol (a2) [isocyanate group. It is preferable that [X] / hydroxyl group [Y]] be 0.90 to 2.0.

  When manufacturing the said urethane resin (A), an organic solvent can also be used as a solvent as above-mentioned. Examples of the organic solvent include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetic esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; amides such as dimethylformamide and N-methylpyrrolidone. Can be used alone or in combination of two or more. The organic solvent is preferably removed by distillation or the like after the urethane resin (A) or composite resin particle (D) is produced.

  The urethane resin (A) obtained by the above method is 5,000 to 500,000 in order to obtain a printed matter excellent in adhesion and printability, a conductive pattern excellent in fine lineability and durability, and the like. Those having a weight average molecular weight are preferably used, and those having a weight average molecular weight of 20,000 to 100,000 are more preferably used.

  The urethane resin (A) obtained by the above method may have various functional groups as necessary. Examples of the functional group include crosslinks such as alkoxysilyl groups, silanol groups, hydroxyl groups, and amino groups. Sex functional group.

  The alkoxysilyl group or silanol group can be introduced into the polyurethane (A) by using γ-aminopropyltriethoxysilane or the like when the urethane resin (A) is produced.

  On the other hand, as the crosslinkable functional group, those which form a crosslink structure by reacting with the crosslinkable functional groups or the crosslinker (E) described later by heating to approximately 100 ° C or higher, preferably 120 ° C or higher are used. be able to.

  Specifically, when a urethane resin having a functional group capable of undergoing a crosslinking reaction by heating to approximately 100 ° C. or higher, preferably 120 ° C. or higher is used, the receptor layer-forming resin composition containing the same is used. The receiving layer constituting the receiving substrate obtained by applying to the substrate and drying or the like does not substantially form a crosslinked structure. After printing on the receiving substrate using the fluid, a crosslinking reaction can be formed by heating or the like to form a crosslinked structure. As a result, in the plating treatment step described later, even when exposed to a plating agent made of a strong alkali or strong acid substance, the remarkably excellent durability does not cause peeling of the receiving layer from the support. A printed matter, a conductive pattern, or the like provided with can be formed.

  The functional group capable of undergoing a crosslinking reaction by heating to 100 ° C. or higher, preferably 120 ° C. or higher, depends on the selection of the crosslinking agent (E) to be used in combination. For example, a crosslinking agent such as a blocked isocyanate compound is used. In some cases, a hydroxyl group or an amino group can be used.

  It is preferable that the said crosslinkable functional group is contained in the range of a total 0.005 equivalent / kg-1.5 equivalent / kg with respect to the whole quantity of the said urethane resin (A).

  Next, the vinyl polymer (B) used for the receiving layer forming resin composition of the present invention will be described.

  It is important to use the vinyl polymer (B) in order to obtain a printed matter such as a conductive pattern excellent in fine line properties.

  As the vinyl polymer (B), it is preferable to use a polymer having a glass transition temperature of 10 ° C. to 70 ° C. in order to form a printed matter excellent in printability, particularly fine lineability. In addition, the glass transition temperature of the said vinyl polymer (B) is a value determined by calculation mainly based on the composition of the vinyl monomer used for manufacture of this vinyl polymer (B). Specifically, the vinyl polymer having the predetermined glass transition temperature can be obtained by using a combination of vinyl monomers described later.

  In addition, when the receptor layer is formed, the receptor layer-forming resin composition has a good film-forming property, and when the receptor substrate is wound around a roll or the like, the receptor layer is laminated. From the viewpoint of providing a level of blocking resistance that does not cause sticking with the back surface of the support constituting the receiving substrate over time, it is possible to use one having a glass transition temperature of 10 ° C to 40 ° C. preferable.

  The vinyl polymer (B) preferably has a weight average molecular weight of 800,000 or more, and has a weight average of 1,000,000 or more in order to form a printed matter having no bleeding and excellent printability. It is more preferable to use one having a molecular weight. The same applies to the formation of a receiving layer of a fluid such as a conductive ink that is free from bleeding and has excellent thin-line properties.

  Although it does not specifically limit as an upper limit of the weight average molecular weight of the said vinyl polymer (B), It is preferable that it is generally 10 million or less, and it is preferable that it is 5 million or less.

  The vinyl polymer (B) may have various functional groups as necessary. Examples of the functional group include an amide group, a hydroxyl group, a glycidyl group, an amino group, a silyl group, and an aziridinyl group. , Crosslinkable functional groups such as isocyanate group, oxazoline group, cyclopentenyl group, allyl group, carboxyl group, and acetoacetyl group.

  The crosslinkable functional group forms a crosslinked structure by printing on the receiving base material using a fluid such as ink and then performing a crosslinking reaction by heating or the like. As a result, even when a solvent such as plating agent or cleaning agent adheres, it has excellent durability that can maintain good electrical conductivity without causing dissolution or peeling of the receptor layer. A printed matter such as a conductive pattern can be formed.

  As the crosslinkable functional group, for example, it is preferable to use one that can form a crosslinked structure by heating to approximately 100 ° C. or higher, preferably 120 ° C. or higher, specifically, methylol. It is preferable to use one or more thermally crosslinkable functional groups selected from the group consisting of amide groups and alkoxymethylamide groups.

  Specific examples of the alkoxymethylamide group include an amide group formed by bonding a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like to a nitrogen atom.

  Moreover, as said crosslinkable functional group, when using the crosslinking agent (E) mentioned later, it is preferable to use a hydroxyl group, a carboxyl group, etc., for example. An amino group can also be used when the conditions for forming the receptor layer can be sufficiently controlled.

  As the vinyl polymer (B), among those described above, it is preferable to use a polymer having at least one selected from the group consisting of a methylolamide group and an alkoxymethylamide group, and the durability of the receiving layer and various supports. It is particularly preferable for greatly improving the adhesion to the body.

  As the vinyl polymer (B), various types can be used. For example, those obtained by radical polymerization of a conventionally known vinyl monomer can be used.

Examples of vinyl monomers that can be used in the production of the vinyl polymer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. i-butyl, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, (Meth) acrylic such as dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate Acid esters; (meth) acrylic acid 2,2,2-trifluoroethyl, (meth) acrylic acid 2,2,3,3- (Meth) acrylic such as n-fluoropropyl, perfluorocyclohexyl (meth) acrylate, 2,2,3,3, -tetrafluoropropyl (meth) acrylate, β- (perfluorooctyl) ethyl (meth) acrylate Acid alkyl esters can be used.

  Among the above, methyl methacrylate is a thin line having a width of about 0.01 μm to 200 μm, preferably about 0.01 μm to 150 μm, which is required when forming a conductive pattern such as an electronic circuit. It is preferable to use it in order to enable printing without causing it (improvement of fine line properties). In addition, for example, the methyl methacrylate is used for imparting excellent adhesion between the receptor layer and the support, regardless of the influence of heat or the like in the baking step when the conductive pattern is produced. Is preferred.

  Moreover, it is preferable to use the (meth) acrylic acid alkyl ester which has a C2-C12 alkyl group with the said methyl methacrylate, Acrylic acid which has a C3-C8 alkyl group It is more preferable to use an alkyl ester, and it is preferable to use n-butyl acrylate in order to obtain a printed matter having excellent printability. Further, even when a conductive ink is used, it is particularly preferable for forming a conductive pattern that is free from bleeding or the like and has excellent thin line properties.

  Moreover, as a vinyl monomer which can be used when producing the vinyl polymer (B), in addition to those described above, acrylic acid, methacrylic acid, (meth) acrylic acid β-carboxyethyl, 2- (meth) Carboxyl groups such as acryloylpropionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride, β- (meth) acryloyloxyethyl hydrogen succinate, etc. The vinyl monomer can be used. The vinyl monomer having a carboxyl group may be neutralized with ammonia, potassium hydroxide, or the like.

  Examples of the other vinyl monomer include one or more amide groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group, an amide group other than the above, and a hydroxyl group in the vinyl polymer (B). From the viewpoint of introducing the crosslinkable functional group such as glycidyl group, amino group, silyl group, aziridinyl group, isocyanate group, oxazoline group, cyclopentenyl group, allyl group, carbonyl group, acetoacetyl group, etc. The vinyl monomer can be used.

  Examples of the vinyl monomer having one or more amide groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group that can be used for the crosslinkable functional group-containing vinyl monomer include N-methylol (meth). Acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyethoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N -N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-pentoxymethyl (meth) acrylamide, N-ethoxymethyl-N-methoxymethyl (meth) acrylamide, N, N'-dimethylol (Meth) acrylic N-ethoxymethyl-N-propoxymethyl (meth) acrylamide, N, N′-dipropoxymethyl (meth) acrylamide, N-butoxymethyl-N-propoxymethyl (meth) acrylamide, N, N-dibutoxymethyl (Meth) acrylamide, N-butoxymethyl-N-methoxymethyl (meth) acrylamide, N, N′-dipentoxymethyl (meth) acrylamide, N-methoxymethyl-N-pentoxymethyl (meth) acrylamide, etc. are used can do.

  Among them, the use of Nn-butoxymethyl (meth) acrylamide and N-isobutoxymethyl (meth) acrylamide makes it possible to produce printed matter with excellent printability and durability, and electrical conductivity with excellent fineness and durability. It is preferable for obtaining a pattern or the like.

  Examples of the vinyl monomer having a crosslinkable functional group include those other than those described above, such as amide group-containing vinyl monomers such as (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic. 2-hydroxypropyl acid, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, Vinyl monomers having a hydroxyl group such as glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, N-hydroxyethyl (meth) acrylamide: glycidyl (meth) acrylate, allyl glycidyl ether (meth) acrylate, etc. Polymerizable monomer having a glycidyl group; amino (meth) acrylate Polymerizable monomers having an amino group such as ethyl, dimethylaminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, N, N-dialkylaminoalkyl (meth) acrylate; vinyltrichlorosilane , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryl Roxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltri Methoxysilane and its hydrochloride A polymerizable monomer having a silyl group; a polymerizable monomer having an aziridinyl group such as 2-aziridinylethyl (meth) acrylate; a phenol or methylethylketo of (meth) acryloyl isocyanate, (meth) acryloyl isocyanate ethyl Polymerizable monomers having isocyanate groups and / or blocked isocyanate groups such as oxime adducts; polymerizable monomers having oxazoline groups such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline; Polymerizable monomers having a cyclopentenyl group such as (meth) acrylate dicyclopentenyl; Polymerizable monomers having an allyl group such as allyl (meth) acrylate; Carbonyl groups such as acrolein and diacetone (meth) acrylamide A polymerizable monomer having .

  In addition to the above-mentioned vinyl monomers, the vinyl monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, hexyl vinyl ether, ( (Meth) acrylonitrile, styrene, α-methylstyrene, vinyltoluene, vinylanisole, α-halostyrene, vinylnaphthalene, divinylstyrene, isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone, polyethylene Glycol mono (meth) acrylate, glycerol mono (meth) acrylate, vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, 2-methyl Ruallylsulfonic acid, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, “Adekaria soap PP-70, PPE-710” (manufactured by Asahi Denka Kogyo Co., Ltd.) or the like Can be used.

  As described above, as the vinyl monomer having a crosslinkable functional group, N-butoxymethyl (meth) acrylamide and N-isobutoxymethyl (meth) acrylamide capable of undergoing a self-crosslinking reaction by heating or the like are used alone or in combination. And (meth) acrylamide, hydroxyl group-containing vinyl monomers such as (meth) acrylic acid 2-hydroxyethyl and (meth) acrylic acid 4-hydroxybutyl are preferably used in combination.

  Moreover, when using the crosslinking agent (E) mentioned later, when introduce | transducing the functional group which can become a crosslinking point with a crosslinking agent (E), for example, a hydroxyl group, (meth) acrylic-acid 2-hydroxyethyl, ( It is more preferable to use 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate. The use of the vinyl monomer having a hydroxyl group is preferable when an isocyanate crosslinking agent is used as the crosslinking agent (E) described later.

  The vinyl monomer having a crosslinkable functional group can be used in the range of 0% by mass to 50% by mass with respect to the total amount of the vinyl monomer mixture. When the crosslinking agent (E) undergoes a self-crosslinking reaction, or when the crosslinking agent (E) reacts with a crosslinkable functional group that the urethane resin (A) can have, the crosslinkable functional group. It is not necessary to use a vinyl monomer having

  Among the vinyl monomers having the crosslinkable functional group, the vinyl monomer having the amide group is based on the total amount of the vinyl monomer mixture when introducing a self-crosslinking reactive methylolamide group or the like. It is preferably used in the range of 0.1% by mass to 50% by mass, and more preferably in the range of 1% by mass to 30% by mass. The vinyl monomer having another amide group used in combination with the self-crosslinking reactive methylolamide group or the vinyl monomer having a hydroxyl group is 0.1% based on the total amount of the vinyl monomer. It is preferable to use in the range of mass% to 30 mass%, and it is more preferable to use in the range of 1 mass% to 20 mass%.

  Of the vinyl monomers having a crosslinkable functional group, the vinyl monomer having a hydroxyl group depends on the type of the crosslinking agent (E) used in combination, but the total amount of the vinyl monomer mixture. In general, it is preferably used in the range of 0.05% by mass to 50% by mass, preferably in the range of 0.05% by mass to 30% by mass, and 0.1% by mass to 10% by mass. More preferably it is used.

  The (meth) acrylic acid alkyl ester is preferably used in the range of 30% by mass to 95% by mass with respect to the total amount of the vinyl monomer mixture used for the production of the vinyl polymer (B). In particular, methyl (meth) acrylate is preferably used in the range of 10% by mass to 70% by mass, more preferably 30% by mass to 65% by mass, based on the total amount of the vinyl monomer mixture, and An acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms, preferably an acrylic acid alkyl ester having an alkyl group having 3 to 8 carbon atoms, more preferably butyl (meth) acrylate is 10 It is used in the range of mass% to 50 mass%.

  The vinyl polymer (B) can be produced by polymerizing a mixture of various vinyl monomers as described above by a conventionally known method, and has excellent printability and fine lineability without blurring. It is preferable to apply an emulsion polymerization method as a means for obtaining a high molecular weight polymer capable of forming a receiving layer capable of forming a printed matter.

  As the emulsion polymerization method, for example, water, a vinyl monomer mixture, a polymerization initiator, and, if necessary, a chain transfer agent, an emulsifier, a dispersion stabilizer, and the like are collectively supplied and mixed in a reaction vessel. A polymerization method, a monomer dropping method in which a vinyl monomer mixture is dropped into a reaction vessel and polymerization, or a vinyl monomer mixture, an emulsifier, etc. and water mixed in advance are dropped into the reaction vessel for polymerization. A pre-emulsion method or the like can be applied.

  The temperature during the emulsion polymerization varies depending on the type of vinyl monomer and polymerization initiator used, but is preferably about 30 ° C. to 90 ° C., for example, and the polymerization time is preferably about 1 hour to 10 hours, for example.

  Examples of the polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, organic peroxides such as benzoyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide, and peroxides. There is hydrogen, etc., and radical polymerization is carried out using only these peroxides, or the above-mentioned peroxides and metal salts of ascorbic acid, erythorbic acid, sodium erythorbate, formaldehyde sulfoxylate, sodium thiosulfate, sodium bisulfite Polymerization can also be achieved by a redox polymerization initiator system in combination with a reducing agent such as ferric chloride, and 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2- It is also possible to use an azo-based initiator such as amidinopropane) dihydrochloride. It may be a good combination of two or more types may be used.

  Examples of the emulsifier that can be used for the production of the vinyl polymer (B) include anionic surfactants, nonionic surfactants, cationic surfactants, and zwitterionic surfactants.

  Examples of the anionic surfactant include sulfates of higher alcohols and salts thereof, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, polyoxyethylene alkyl diphenyl ether sulfonates, and polyoxyethylene alkyl ethers. Examples include non-ionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl phenyl ether. Ethylene diphenyl ether, polyoxyethylene-polyoxypropylene block copolymer, acetylenic diol surfactant and the like can be used.

  Moreover, as said cationic surfactant, alkyl ammonium salt etc. can be used, for example.

  In addition, as the zwitterionic surfactant, for example, alkyl (amido) betaine, alkyldimethylamine oxide and the like can be used.

  As the emulsifier, in addition to the above-mentioned surfactants, fluorine-based surfactants, silicone-based surfactants, and emulsifiers having a polymerizable unsaturated group generally called “reactive emulsifier” in the molecule Can also be used.

  Examples of the reactive emulsifier include “Latemul S-180” (manufactured by Kao Corporation) having a sulfonic acid group and a salt thereof, “Eleminol JS-2, RS-30” (manufactured by Sanyo Chemical Industries, Ltd.) and the like; “Aqualon HS-10, HS-20, KH-1025” (Daiichi Kogyo Seiyaku Co., Ltd.), “Adekaria Soap SE-10, SE-20” (Asahi Denka Kogyo Co., Ltd.) having a sulfate group and a salt thereof "New Frontier A-229E" having a phosphate group (Daiichi Kogyo Seiyaku Co., Ltd.), etc .; "Aqualon RN-10, RN-20, RN-30, RN-50 having a nonionic hydrophilic group" (Daiichi Kogyo Seiyaku Co., Ltd.) can be used.

  Moreover, as an aqueous medium used for manufacture of the said vinyl polymer (B), the thing similar to what was illustrated as an aqueous medium (C) mentioned later can be used.

  Moreover, as a chain transfer agent which can be used for manufacture of the said vinyl polymer (B), a lauryl mercaptan etc. can be used and it is 0 mass%-1.0 mass with respect to the whole quantity of the said vinyl monomer mixture. % Is preferable, and the range of 0% by mass to 0.5% by mass is more preferable.

  The resin composition for forming a receiving layer in which the urethane resin (A) and the vinyl polymer (B) are independently present in the aqueous medium (C) is, for example, an aqueous dispersion of the urethane resin (A) obtained above. It can manufacture by mixing a body and the aqueous dispersion of the said vinyl polymer (B).

  Moreover, the resin composition for receiving layer formation containing the composite resin particle (D) formed with the said urethane resin (A) and the said vinyl polymer (B) can be manufactured, for example with the following method.

  For example, as described above, the composite resin particle (D) is obtained by reacting the polyisocyanate (a1), the polyol (a2) and, if necessary, a chain extender and dispersing in water to thereby form a urethane resin (A). The water dispersion can be produced by a step (W) for producing an aqueous dispersion, and a step (Y) for producing a vinyl polymer (B) by polymerizing the vinyl monomer in the aqueous dispersion.

  Specifically, the urethane resin (A) is obtained by reacting the polyisocyanate (a1) with the polyol (a2) in the absence of a solvent or in an organic solvent or in the presence of a reactive diluent such as a vinyl monomer. Next, a part or all of the hydrophilic group of the urethane resin (A) is neutralized with a basic compound or the like as necessary, and further reacted with a chain extender as necessary. Then, an aqueous dispersion of the urethane resin (A) is produced by dispersing it in the aqueous medium (D).

  Next, the vinyl monomer is supplied into the aqueous dispersion of the urethane resin (A) obtained above, and the vinyl monomer is radically polymerized in the urethane resin (A) particles to give a vinyl polymer (B ).

  Thereby, a resin composition for forming a receiving layer in which the composite resin particles (D) in which the vinyl polymer (B) is contained in the urethane resin (A) particles is dispersed in an aqueous medium (C) can be produced. it can.

  When the composite resin particles (D) are produced, if the urethane resin (A) has a high viscosity and is not excellent in workability, the usual resin such as methyl ethyl ketone, N-methylpyrrolidone, acetone, dipropylene glycol dimethyl ether, etc. Organic solvents and reactive diluents can be used. In particular, the use of a vinyl monomer that can be used for the production of the vinyl polymer (B) as the reactive diluent improves the production efficiency of the resin composition for forming the receiving layer by omitting the solvent removal step. It is preferable when aiming at.

  Examples of the aqueous medium (C) in which the urethane resin (A), the vinyl polymer (B), or the composite resin particles (D) obtained by the above reaction can be dispersed or dissolved include water and organic solvents miscible with water. And mixtures thereof. Examples of organic solvents miscible with water include alcohols such as methanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycols And lactams such as N-methyl-2-pyrrolidone, and the like. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.

  The aqueous medium (C) is preferably contained in an amount of 50% by mass to 90% by mass, and more preferably 65% by mass to 85% by mass with respect to the total amount of the resin composition for forming a receiving layer.

  In addition, as the resin composition for forming a receiving layer of the present invention, in order to further improve the printability and fine lineability when using a fluid such as an aqueous pigment ink, a conductive ink, or a plating nucleating agent, A combination of water-soluble resins can be used.

  Examples of the water-soluble resin include polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal, polyalkylene oxide, starch, methylcellulose, hydroxycellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose and other cellulose derivatives, polyethyleneimine, polyamide, various Quaternary ammonium base-containing water-soluble resins, modified products thereof, and the like can be used. Among these, it is preferable to use polyvinyl alcohol.

  In addition, the resin composition for forming a receiving layer of the present invention includes a crosslinking agent (E), a pH adjuster, a film-forming aid, a leveling agent, a thickening agent as necessary, as long as the effects of the present invention are not impaired. Known agents such as agents, water repellents, and antifoaming agents may be added as appropriate.

  Examples of the crosslinking agent (E) include a metal chelate compound, a polyamine compound, an aziridine compound, a metal salt compound, and an isocyanate compound that can react at a relatively low temperature of approximately 25 ° C. to less than 100 ° C. to form a crosslinked structure. It reacts at a relatively high temperature of about 100 ° C. or higher, such as one or more selected from the group consisting of a crosslinking agent (e1-1), a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a blocked isocyanate compound. A thermal crosslinking agent (e1-2) capable of forming a crosslinked structure and various photocrosslinking agents can be used.

  In the case of a resin composition for forming a receiving layer containing the thermal crosslinking agent (e1-1), for example, it is applied to the surface of a support, dried at a relatively low temperature, and then printed using the fluid. After that, by forming a cross-linked structure by heating to a temperature of less than 100 ° C., it has excellent durability with a level that can prevent the loss of conductive substances and pigments regardless of the influence of heat and external force over a long period of time. An ink-receiving substrate having properties can be formed.

  On the other hand, if it is a resin composition for forming a receiving layer containing the thermal crosslinking agent (e1-2), for example, it is applied to the support surface and dried at a low temperature of room temperature (25 ° C.) to less than about 100 ° C. Then, after manufacturing an ink receiving substrate that does not form a cross-linked structure and then printing using ink or the like, the cross-linked structure is formed by heating at a temperature of, for example, 100 ° C. or higher, preferably 120 ° C. or higher. As a result, it is possible to obtain a printed matter or a conductive pattern having exceptionally excellent durability that does not cause ink peeling or the like regardless of the influence of heat, external force, or the like over a long period of time.

  Examples of the metal chelate compound that can be used for the thermal crosslinking agent (e1-1) include acetylacetone of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. Coordination compounds, acetoacetate coordination compounds and the like can be used, and it is preferable to use acetylacetone aluminum which is an acetylacetone coordination compound of aluminum.

  Moreover, as a polyamine compound which can be used for the said thermal crosslinking agent (e1-1), tertiary amines, such as a triethylamine, a triethylenediamine, a dimethylethanolamine, can also be used, for example.

  Examples of the aziridine compound that can be used for the thermal crosslinking agent (e1-1) include 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 1,6-hexamethylenediethylene urea. Diphenylmethane-bis-4,4′-N, N′-diethyleneurea and the like can be used.

  Examples of the metal salt compound that can be used as the crosslinking agent (e1-1) include aluminum sulfate, aluminum alum, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, and aluminum chloride hexahydrate. Water-soluble metal salts such as aluminum-containing compounds such as titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate, and titanium lactate can be used.

  Examples of isocyanate compounds that can be used in the thermal crosslinking agent (e1-1) include tolylene diisocyanate, hydrogenated tolylene diisocyanate, triphenylmethane triisocyanate, methylene bis (4-phenylmethane) triisocyanate, isophorone diisocyanate, hexamethylene. A polyisocyanate such as diisocyanate and xylylene diisocyanate, an isocyanurate type polyisocyanate compound obtained by using them, an adduct comprising them and trimethylolpropane, the polyisocyanate compound and a polyol such as trimethylolpropane. Polyisocyanate group-containing urethane obtained by reacting can be used. Among them, hexamethylene diisocyanate nurate, adduct of hexamethylene diisocyanate and trimethylolpropane, adduct of tolylene diisocyanate and trimethylolpropane, adduct of xylylene diisocyanate and trimethylolpropane, etc. are used. It is preferable.

  Examples of the melamine compound that can be used in the thermal crosslinking agent (e1-2) include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentyloxymethyl melamine, and hexahexyl. Oxymethyl melamine or a mixed etherified melamine obtained by combining these two types can be used. Of these, trimethoxymethyl melamine and hexamethoxymethyl melamine are preferably used. As a commercial item, becamine M-3, APM, J-101 (made by DIC Corporation) etc. can be used. The melamine compound can form a crosslinked structure by a self-crosslinking reaction.

  When the melamine compound is used, a catalyst such as an organic amine salt may be used to promote the self-crosslinking reaction. As a commercial item, catalyst ACX, 376 etc. can be used. The catalyst is preferably in the range of approximately 0.01% by mass to 10% by mass with respect to the total amount of the melamine compound.

  Examples of the epoxy compound that can be used for the thermal crosslinking agent (e1-2) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, cyclohexanediol diglycidyl ether, and glycerin diglycidyl ether. , Polyglycidyl ethers of aliphatic polyhydric alcohols such as glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether; polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether Polyglycidyl ethers of polyalkylene glycols such as 1,3-bis (N, N -Polyglycidylamines such as diglycidylaminoethyl) cyclohexane; polyglycidyl esters of polycarboxylic acids [succinic acid, adipic acid, butanetricarboxylic acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, benzenetricarboxylic acid, etc.] Bisphenol A-based epoxy resins such as condensates of bisphenol A and epichlorohydrin, ethylene oxide adducts of condensates of bisphenol A and epichlorohydrin, phenol novolac resins, various vinyl (co) polymers having an epoxy group in the side chain, etc. Can be used. Among these, it is preferable to use polyglycidylamines such as 1,3-bis (N, N′-diglycidylaminoethyl) cyclohexane and polyglycidyl ethers of aliphatic polyhydric alcohols such as glycerin diglycidyl ether.

  Examples of the epoxy compound include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxypropyl other than those described above. Methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane Alternatively, a glycidyl group-containing silane compound such as γ-glycidoxypropyltriisopropenyloxysilane can also be used.

  Examples of the oxazoline compound that can be used in the thermal crosslinking agent (e1-2) include 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2-oxazoline), 2 , 2'-ethylene-bis- (2-oxazoline), 2,2'-trimethylene-bis- (2-oxazoline), 2,2'-tetramethylene-bis- (2-oxazoline), 2,2'- Hexamethylene-bis- (2-oxazoline), 2,2′-octamethylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (4,4′-dimethyl-2-oxazoline), 2 , 2'-p-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (4,4'- Dimethyl-2-oxazo Emissions), bis - (2-oxazolinyl sulfonyl cyclohexane) sulfide, bis - (2-oxazolinyl sulfonyl norbornane) can be used sulfides.

  In addition, as the oxazoline compound, for example, an oxazoline group-containing polymer obtained by combining and polymerizing the following addition polymerizable oxazoline and, if necessary, other monomers can also be used.

  Examples of the addition polymerizable oxazoline include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. , 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, etc., alone or in combination. Can do. Among them, it is preferable to use 2-isopropenyl-2-oxazoline because it is easily available industrially.

  Examples of the carbodiimide compound that can be used for the thermal crosslinking agent (e1-2) include poly [phenylenebis (dimethylmethylene) carbodiimide] and poly (methyl-1,3-phenylenecarbodiimide). . Commercially available products include Carbodilite V-01, V-02, V-03, V-04, V-05, V-06 (manufactured by Nisshinbo Co., Ltd.), UCALINK XL-29SE, XL-29MP (manufactured by Union Carbide Corporation). Etc. can be used.

  Moreover, as a blocked isocyanate compound which can be used for the said thermal crosslinking agent (e1-2), a part or all of the isocyanate group which the isocyanate compound illustrated as the said thermal crosslinking agent (e1-1) has is made into a blocking agent. What was sealed can be used.

  Examples of the blocking agent include phenol, cresol, 2-hydroxypyridine, butyl cellosolve, propylene glycol monomethyl ether, benzyl alcohol, methanol, ethanol, n-butanol, isobutanol, dimethyl malonate, diethyl malonate, methyl acetoacetate, Ethyl acetoacetate, acetylacetone, butyl mercaptan, dodecyl mercaptan, acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, succinimide, maleic imide, imidazole, 2-methylimidazole, urea, thiourea, Ethyleneurea, formamide oxime, acetaldoxime, acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexano Oxime, diphenyl aniline, can be used aniline, carbazole, ethyleneimine, polyethyleneimine and the like.

  As the blocked isocyanate compound, Elastolon BN-69 (Daiichi Kogyo Seiyaku Co., Ltd.) can be used as a water-dispersed commercial product.

  When using the said crosslinking agent (E), it is preferable to use what has a group which can react with the crosslinkable functional group which the said crosslinking agent (E) has as said vinyl resin (B). Specifically, it is preferable to use the (block) isocyanate compound, the melamine compound, the oxazoline compound, and the carbodiimide compound as a crosslinking agent, and use a vinyl resin having a hydroxyl group or a carboxyl group as the vinyl resin (A).

  Although the said crosslinking agent (E) changes with kinds etc., it is 0. 0 normally with respect to 100 mass parts of total mass of the said urethane resin (A), the said vinyl polymer (B), and the said composite resin particle (D). It is preferably used in the range of 01% by mass to 60% by mass, more preferably in the range of 0.1% by mass to 10% by mass, and in the range of 0.1% by mass to 5% by mass. However, it is preferable for forming a receiving layer capable of forming a printed image having excellent printability. In addition, even when forming a conductive pattern using conductive ink or the like, the level that can be used to realize higher density of electronic circuits or the like without causing bleeding of printed portions such as fine lines is much better. It is preferable because it can provide fine lineability and can further improve the adhesion between the receptor layer and the support.

  The crosslinking agent (E) is preferably added and used in advance before coating or impregnating the support layer-forming resin composition of the present invention on the support surface.

  Further, as the resin composition for forming a receiving layer of the present invention, in addition to the above-mentioned additives, solvent-soluble or solvent-dispersible thermosetting resins, such as phenol resins, urea resins, melamine resins, polyester resins, A polyamide resin, a urethane resin, or the like can be mixed and used.

  Moreover, as said additive, various fillers, such as an inorganic particle, can also be used. However, as the receiving layer forming resin composition of the present invention, the amount of the filler used is preferably as small as possible, and is 5% by mass or less based on the total amount of the receiving layer forming resin composition of the present invention. It is more preferable.

  Although the usage-amount of the said additive will not be specifically limited if it is a range which does not impair the effect of this invention, 0.01 mass%-40 mass with respect to the total amount of solid content in the resin composition for electroconductive receiving layer formation % Is preferable.

  The receptor layer that can be formed using the resin composition for forming the receptor layer is composed of a urethane resin (A), a vinyl polymer (B), and composite resin particles (D) constituting the receptor layer in a fluid such as ink. It is a swellable type that can be accurately fixed to the surface of the ink receiving layer by dissolving a suitable amount of the solvent and absorbing the solvent to absorb the solvent. Therefore, it is possible to obtain a printed matter such as a conductive pattern without bleeding. In addition, the resin composition for forming a receiving layer of the present invention can form a transparent receiving layer as compared with a conventionally known porous type receiving layer.

  Next, the receiving substrate for the fluid according to the present invention will be described.

  The receiving substrate of the present invention has a receiving layer formed by using the receiving layer forming resin composition on a part or all of the surfaces of various supports and on one or both sides of the support.

  The receiving layer is a layer that absorbs a solvent in the fluid when the fluid is in contact with the surface of the receiving layer and carries a conductive substance or pigment on the surface of the receiving layer. For example, if a pigment ink is used as the fluid, it is possible to form a highly clear printed matter without bleeding, and if a conductive ink is used as the fluid, a conductive pattern without bleeding. If a plating nucleating agent is used as the fluid, a laminated body in which the plating nuclei are uniformly supported on the surface of the receiving layer can be formed.

  The receptor layer may be laminated on the support, but a part of the receptor layer may be impregnated in the support.

  The receiving substrate of the present invention is coated with the receiving substrate on one or both sides of the support, or, when the support is a fiber substrate or the like, impregnated in the support to form the receiving layer. It can manufacture by volatilizing the aqueous medium (C) contained in a resin composition.

  Examples of the support include fine paper, coated paper, polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (ABS), poly (meth) acrylic. A support made of acrylic resin such as methyl acid, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene, polypropylene, polyurethane, cellulose nanofiber, silicon, ceramics, glass, etc. A support made of a metal such as a support, a steel plate or copper can be used.

  In addition, as the support, for example, a base material made of synthetic fibers such as polyester fibers, polyamide fibers, and aramid fibers, natural fibers such as cotton and hemp can be used. The fibers may be processed in advance.

  As a method for coating or impregnating the receptor layer-forming resin composition on the support, known and conventional methods can be used, for example, gravure method, coating method, screen method, roller method, rotary method, A spray method or the like can be applied.

  The method for volatilizing the aqueous medium (C) contained in the receptor layer after coating or impregnating the receptor layer-forming resin composition of the present invention on the support is not particularly limited. However, for example, a method of drying using a dryer is common. The drying temperature may be set to a temperature that can volatilize the aqueous medium (C) and does not adversely affect the support.

  Further, as a method for removing a solvent such as a solvent that may be contained in the resin composition after coating or impregnating the support layer-forming resin composition of the present invention to a part or all of the support surface, Although not limited, for example, a method of drying using a dryer is common. The drying temperature may be set to a temperature that can volatilize the solvent and does not adversely affect the support. Specifically, when the thermal crosslinking agent (e1-1) is used, it is preferably dried at a temperature of approximately 25 ° C. to less than 100 ° C., and when the thermal crosslinking agent (e1-2) is used. Is approximately 100 ° C or higher, preferably about 120 ° C to 300 ° C. On the other hand, in the case where the thermal crosslinking agent (e1-2) is used and a crosslinked structure is to be formed after printing using a fluid such as ink, room temperature (25 ° C.) to about 100 ° C. It is preferable to adjust so that it is dried at a relatively low temperature and does not form a crosslinked structure before printing.

The amount of the resin composition for forming the receiving layer on the support is 3 to 60 g relative to the area of the support from the viewpoint of maintaining a very high level of color development and maintaining good production efficiency. / M ² is preferable, and 20 to 40 g / m ² is particularly preferable in consideration of the absorbability of the solvent contained in the fluid and the production cost.

  Moreover, the coloring property of the obtained printed matter can be further improved by increasing the adhesion amount of the resin composition for forming a receiving layer on the support. However, since the texture of the printed matter tends to be slightly harder as the adhesion amount increases, it is preferable to adjust appropriately according to the use purpose of the printed matter.

  Therefore, since the receiving substrate of the present invention can form a printed image having excellent printability and water resistance without causing bleeding or cracking, it can be used for indoor and outdoor advertisements such as signboards, body advertisements, and banners. It can be used.

  The fluid that can be used for printing on the receiving substrate has a viscosity of about 0.1 mPa · s to 500,000 mPa · s, preferably 0.5 mPa · s to 10,000, as measured with a B-type viscometer at 25 ° C. A liquid or viscous liquid having a viscosity of 000 mPa · s, in which a conductive substance, a pigment, or the like is dispersed in a solvent. When the fluid is printed by an inkjet printing method, it is preferable to use a fluid having a viscosity range of 0.5 mPa · s to 10000 mPa · s.

  Specific examples of the fluid include printing inks such as conductive inks and pigment inks, and plating nucleating agents that may be used when plating is performed.

  Examples of the fluid include an aqueous pigment ink in which a pigment is dispersed in an aqueous medium.

  As the aqueous medium, only water may be used, or a mixed solution of water and a water-soluble solvent may be used. Examples of the water-soluble solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve, and polar solvents such as N-methylpyrrolidone.

  Examples of the pigment that can be dispersed or dissolved in the aqueous medium include, for example, quinacridone, anthraquinone, perylene, perinone, diketopyrrolopyrrole, isoindolinone, condensed azo, benzimidazolone, and monoazo. , Organic pigments such as insoluble azo, naphthol, flavanthrone, anthrapyrimidine, quinophthalone, pyranthrone, pyrazolone, thioindigo, anthanthrone, dioxazine, phthalocyanine, indanthrone, nickel dioxin Metal complexes such as yellow and copper azomethine yellow, metal oxides such as titanium oxide, iron oxide and zinc oxide, metal salts such as barium sulfate and calcium carbonate, inorganic pigments such as carbon black and mica, metal fine powder such as aluminum and mica Fine powder etc. can be used . The pigment is preferably used in an amount of 0.5 to 15% by weight, more preferably 1 to 10% by weight, based on the total amount of the aqueous pigment ink.

  As the fluid, a solvent-based pigment ink in which a pigment or the like is dissolved or dispersed in a solvent made of an organic solvent can also be used.

  As the organic solvent, for example, from the viewpoint of preventing drying and clogging of the inkjet head, alcohols, ethers, esters, ketones and the like having a boiling point of 100 to 250 ° C. are preferably used, and boiling points of 120 to 220 are used. More preferred is one at ° C.

  Examples of the alcohols that can be used include ethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, and dipropylene glycol.

  Examples of ethers include ethylene glycol mono (methyl, ethyl, butyl, phenyl, benzyl, ethylhexyl) ether, ethylene glycol di (methyl, ethyl, butyl) ether, diethylene glycol mono (methyl, ethyl, butyl) ether, diethylene glycol di- (Methyl, ethyl, butyl) ether, tetraethylene glycol mono (methyl, ethyl, butyl) ether, tetraethylene glycol di (methyl, ethyl, butyl) ether, propylene glycol mono (methyl, ethyl, butyl) ether, dipropylene glycol Mono (methyl, ethyl) ether, tripropylene glycol monomethyl ether, and the like can be used.

  Examples of the esters include ethylene glycol mono (methyl, ethyl, butyl) ether acetate, ethylene glycol di (methyl, ethyl, butyl) ether acetate, diethylene glycol mono (methyl, ethyl, butyl) ether acetate, diethylene glycol di (methyl, Ethyl, butyl) ether acetate, propylene glycol mono (methyl, ethyl, butyl) ether acetate, dipropylene glycol mono (methyl, ethyl) ether acetate, tripropylene glycol monomethyl ether acetate, 2- (methoxy, ethoxy, butoxy) ethyl acetate , 2-ethylhexyl acetate, dimethyl phthalate, diethyl phthalate, butyl lactate and the like. Examples of ketones include cyclohexanone.

  Of these, diethylene glycol diethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether acetate are preferably used.

  As the pigment used in the solvent-based pigment ink, the same pigments exemplified as those usable in the aqueous pigment ink can be used.

  The receiving substrate of the present invention can be suitably used particularly when printing is performed using a solvent-based pigment ink among the pigment inks composed of the water-based pigment ink and the solvent-based pigment ink.

  Various printing methods can be applied as a method for printing on the receiving substrate of the present invention using the pigment ink, but it is preferable to employ an inkjet printing method, a screen printing method, a letterpress reverse printing method, or a gravure offset printing method. .

  Further, the receiving substrate of the present invention has excellent printability for conductive ink containing a conductive substance as the fluid, and is required when forming a conductive pattern such as an electronic circuit, for example. It is possible to print fine lines having a width of about 0.01 μm to 200 μm, preferably about 0.01 μm to 150 μm without causing bleeding (thin lineability). Therefore, the receiving substrate of the present invention is formed of electronic circuits using silver ink or the like, formation of organic solar cells or electronic book terminals, organic EL, organic transistors, flexible printed boards, RFID, etc. It can also be suitably used in the field of printed electronics such as wiring for electromagnetic shielding of plasma displays.

  The receiving base material (conductive ink receiving base material) of the present invention that can be used for forming the conductive pattern is similar to the above, and the resin composition for forming a receiving layer is formed on part or all of the surface of various supports. It has a receiving layer formed using a thing. The receptor layer may be laminated on a support, but a part of the receptor layer may be impregnated in the support. Moreover, the said receiving layer may be provided in either the single side | surface or both surfaces of a support body, and may be apply | coated to the one part or all part of the surface.

  In the receiving substrate of the present invention, the receiving resin composition for forming a receiving layer is coated and impregnated on a part or all of one side or both sides of a support, and then the resin composition for forming a conductive receiving layer is contained in the resin composition for forming a conductive receiving layer. It can manufacture by removing the aqueous medium (C) contained.

  Examples of the support suitable for laminating the receptor layer in the production of the conductive pattern include polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene- Acrylic resins such as styrene (ABS) and poly (meth) methyl acrylate, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, polyethylene, polypropylene, polyurethane, cellulose nanofiber, silicon, ceramics, glass, etc. Supports made of these materials, porous supports made of these materials, supports made of metals such as steel plates and copper, and the like can be used.

  Among these, as the support, generally used as a support in forming a conductive pattern such as a circuit board, from polyimide resin, polyethylene terephthalate, polyethylene naphthalate, glass, cellulose nanofiber, etc. It is preferable to use a support.

  Moreover, since the base material which consists of a polyimide resin, a polyethylene terephthalate, a polyethylene naphthalate, a polycarbonate, an acrylonitrile-butadiene-styrene (ABS), an acrylic resin, glass etc. among the said support bodies is generally difficult adhesion, resin etc. Is often difficult to adhere.

  In addition, when the support is used for applications that require flexibility, it is possible to use a material that is relatively flexible and capable of being bent. It is preferable for obtaining a final product. Specifically, it is preferable to use a film or sheet-like support formed by uniaxial stretching or the like.

  Examples of the film or sheet-like support include a polyethylene terephthalate film, a polyimide film, and a polyethylene naphthalate film.

  As a method of applying or impregnating the receptor layer-forming resin composition to a part or the whole of the support surface, a known and commonly used method can be used. For example, a gravure method, a coating method, a screen method, A roller method, a rotary method, a spray method, an ink jet method, or the like can be applied.

  In addition, as a method of removing the aqueous medium (C) that can be contained in the resin composition after coating or impregnating part or all of the surface of the support with the resin composition for forming a receiving layer of the present invention, Although not particularly limited, for example, a method of drying using a dryer is common. The drying temperature may be set to a temperature that can volatilize the solvent and does not adversely affect the support.

The amount of the resin composition for forming the receiving layer on the surface of the support is determined by taking into consideration the amount of the solvent contained in the fluid such as conductive ink, the thickness of the conductive pattern, etc. against the resin ^solids, 0.01 g / m 2 is preferably in the range of to 20 g / ^{m 2,} in consideration of the absorbent and the manufacturing cost of the solvent in the fluid 0.01g ^/ m 2 ~10g ^/ m ² is particularly preferred.

Moreover, the fine-line property of a receiving base material can be improved further by making the adhesion amount of the said resin composition for receiving layer formation to the support body surface increase. However, when the adhesion amount increases, the texture of the receiving base material tends to become slightly hard. For example, when good flexibility such as a flexible printed board that can be bent is required, approximately 0.020.1 g / it is preferable that the ^{m 2} ~10g / m ² about relatively thin. On the other hand, depending on the use or the like, generally may be used in ^10g / ^{m 2 ~100g} / m 2 approximately embodiments relatively becomes thick.
→ The lower limit of film thickness has been changed.

  The receiving substrate of the present invention obtained by the above method can be suitably used even when a conductive ink is used as the fluid. For example, in the printed electronics field described above, it is suitable only for the formation of a conductive pattern or the like. Can be used for More specifically, it can be suitably used for a circuit forming substrate used for an electronic circuit, an integrated circuit, or the like.

  The receiving substrate and the circuit forming substrate can be printed using a conductive ink as the fluid. Specifically, printing is carried out using a conductive ink on the receiving layer constituting the receiving substrate, and then a baking step is performed, for example, in the conductive ink on the receiving substrate. A conductive pattern made of a conductive material made of a metal such as silver can be formed.

As the conductive ink that can be used as the fluid, the viscosity measured with a B-type viscometer at about 25 ° C. is generally 0.1 mPa · s to 500,000 mPa · s, preferably 0. It refers to a liquid or viscous liquid that is 5 mPa · s to 10,000 mPa · s, in which conductive substances, pigments, and the like are dispersed in a solvent. When the fluid is printed by an inkjet printing method, it is preferable to use a fluid having a viscosity range of 0.5 mPa · s to 10000 mPa · s.
As the conductive ink, for example, an ink containing a conductive substance, a solvent, and, if necessary, an additive such as a dispersant can be used.

  As the conductive substance, a transition metal or a compound thereof can be used. Among them, it is preferable to use an ionic transition metal, for example, it is preferable to use a transition metal such as copper, silver, gold, nickel, palladium, platinum, cobalt, and to use silver, gold, copper, or the like. It is more preferable because a conductive pattern having low electric resistance and strong against corrosion can be formed.

  As the conductive substance, it is preferable to use a particulate substance having an average particle diameter of about 1 nm to 50 nm. In addition, the said average particle diameter means a center particle diameter (D50), and shows the value at the time of measuring with a laser diffraction scattering type particle size distribution measuring apparatus.

  The conductive material such as metal is preferably included in the range of 10% by mass to 60% by mass with respect to the total amount of the conductive ink.

  As the solvent used for the conductive ink, various organic solvents and an aqueous medium such as water can be used. The receiving substrate of the present invention can be suitably used when a solvent-based conductive ink is used.

  In the present invention, a solvent-based conductive ink mainly containing an organic solvent as a solvent of the conductive ink, an aqueous conductive ink mainly containing water as the solvent, and a conductive containing both the organic solvent and water. A suitable ink can be selected and used.

  Among these, from the viewpoint of improving the fineness and adhesion of the conductive pattern to be formed, the conductive ink containing both the organic solvent and water as the solvent of the conductive ink, and the solvent of the conductive ink It is preferable to use a solvent-based conductive ink mainly containing an organic solvent, and it is more preferable to use a solvent-based conductive ink mainly containing an organic solvent as the solvent of the conductive ink.

  In particular, the receiving layer of the receiving substrate of the present invention is used only as the organic solvent in combination with a conductive ink containing a polar solvent. This is preferable because it is possible to achieve a level of fineness that can be used for realizing higher density of electronic circuits and the like.

  Examples of the solvent used in the solvent-based conductive ink include methanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, and undecanol. , Dodecanol, tridecanol, tetradecanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydroterpineol and other alcohol solvents, 2-ethyl 1,3-hexanediol, ethylene glycol, diethylene glycol, tri Ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol Glycol solvents such as 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl Ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol Rudibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, di Glycols such as propylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol diacetate, propylene glycol phenyl ether, dipropylene glycol dimethyl ether A polar solvent such as an ether ether solvent and glycerin can be used.

  Among the polar solvents, use of a solvent having a hydroxyl group prevents bleeding and fine lineability of a conductive pattern and the like, and lack of a conductive substance contained in the conductive ink from the surface of the receiving layer. It is preferable for preventing the above.

  The solvent-based conductive ink may be used in combination with a ketone-based solvent such as acetone, cyclohexanone, methyl ethyl ketone, etc., for adjusting physical properties. In addition, ester solvents such as ethyl acetate, butyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-butyl acetate, hydrocarbon solvents such as toluene, particularly hydrocarbon solvents having 8 or more carbon atoms, For example, nonpolar solvents such as octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, mesitylene, ethylbenzene, dodecylbenzene, tetralin, and trimethylbenzenecyclohexane can be used in combination as necessary. Furthermore, solvents such as mineral spirits and solvent naphtha, which are mixed solvents, can be used in combination.

  However, since the receiving layer formed using the resin composition for forming a receiving layer of the present invention is particularly preferably used in combination with a conductive ink containing a polar solvent, the nonpolar solvent is contained in the conductive ink. It is more preferable that it is 0 mass%-40 mass% with respect to the whole quantity of the solvent contained in.

  As the aqueous medium that can be used as the solvent of the conductive ink, the same medium as the aqueous medium (C) can be used. For example, only water may be used, or water and a water-soluble medium may be used. A mixed solution of an ionic solvent may be used. Examples of the water-soluble solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, butyl cellosolve, and polar solvents such as N-methylpyrrolidone. It is preferable in terms of preventing the fine line property and the loss of the conductive substance contained in the conductive ink from the surface of the receiving layer.

  The solvent contained in the conductive ink is preferably contained in the range of 40% by mass to 90% by mass with respect to the total amount of the conductive ink. Moreover, it is preferable that the said polar solvent is contained 40 mass%-100 mass% with respect to the whole quantity of the said solvent.

  In addition to the metal and the solvent, various additives can be used as necessary for the conductive ink.

  As the additive, for example, a dispersant can be used from the viewpoint of improving dispersibility of the metal in the solvent.

  Examples of the dispersant include amine-based polymer dispersants such as polyethyleneimine and polyvinylpyrrolidone, hydrocarbon-based polymer dispersants having a carboxylic acid group in the molecule such as polyacrylic acid and carboxymethylcellulose, and polyvinyl alcohol. A polymer dispersant having a polar group, such as a styrene-maleic acid copolymer, an olefin-maleic acid copolymer, or a copolymer having a polyethyleneimine moiety and a polyethylene oxide moiety in one molecule. Can do. The polyvinyl alcohol may be used as a dispersant even when a solvent-based conductive ink is used.

  Examples of a method for printing on the receiving substrate using the conductive ink include, for example, an ink jet printing method, a screen printing method, a letterpress reverse printing method or a gravure offset printing method, an offset printing method, a spin coating method, and a spray coating method. , Bar coating method, die coating method, slit coating method, roll coating method, dip coating method and the like.

  As the ink jet printing method, what is generally called an ink jet printer can be used. Specific examples include Konica Minolta EB100 and XY100 (manufactured by Konica Minolta IJ Co., Ltd.), Dimatics Material Printer DMP-3000, Dimatics Material Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.), and the like. .

  The screen printing method is a method in which a conductive ink is applied to the surface of the receiving layer by using a mesh screen plate. Specifically, a conductive pattern having a predetermined pattern shape can be formed by printing a conductive pattern in a predetermined pattern shape using a metal screen plate generally called a metal mesh.

  The letterpress reverse printing method is a method in which a conductive ink is applied on a blanket to form a conductive ink application surface, which is transferred to the receiving layer.

  As the blanket, it is preferable to use a silicone blanket made of silicone.

  First, conductive ink is applied on the blanket to form a layer made of conductive ink. Next, the conductive ink contacting the relief plate is transferred from the blanket onto the relief plate surface by pressing a relief plate provided with a plate corresponding to a predetermined pattern shape as necessary to the layer made of the conductive ink. Is done.

  Next, the conductive ink remaining on the blanket is transferred to the surface of the receiving layer by bringing the blanket into contact with the receiving layer. By such a method, a conductive pattern having a predetermined pattern can be formed.

  Further, as the gravure offset printing method, for example, after supplying conductive ink to a groove portion of an intaglio printing plate having a predetermined pattern shape, the conductive ink is applied onto the blanket by pressing the blanket on the surface thereof. And then transferring the conductive ink on the blanket to the receiving layer.

  As the intaglio printing plate, for example, a gravure plate, a glass intaglio plate formed by etching a glass plate, or the like can be used.

  As the blanket, a blanket having a multilayer structure including a silicone rubber layer, a polyethylene terephthalate layer, a sponge-like layer, etc. can be used and is usually wound around a rigid cylinder called a blanket cylinder. Is used.

Conductivity can be imparted to the printed matter printed by the above-described method on the receiving substrate by closely contacting and joining the conductive substances contained in the conductive ink.
Examples of the method for bonding the conductive substances include a heat baking method and a light irradiation method.

  The firing is preferably performed in the range of approximately 80 ° C. to 300 ° C. for approximately 2 minutes to 200 minutes. The calcination may be performed in the air, but part or all of the calcination step may be performed in a reducing atmosphere from the viewpoint of preventing oxidation of the metal.

  The firing step can be performed using, for example, an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, flash lamp irradiation, microwave, or the like.

  In addition, when the cross-linking agent (e1-2) is used and a cross-linked structure is to be formed after printing using a conductive ink or the like, a cross-linked structure is formed after printing by passing through the baking step. Is done. Thereby, durability of printed matter, such as a conductive pattern, can be improved to each step.

  When the crosslinking reaction and the baking step are carried out, the heating temperature varies depending on the type of the crosslinking agent (E) used, the combination of crosslinkable functional groups, and the like, but is generally in the range of 80 ° C to 300 ° C. It is preferable, 100 to 300 ° C is more preferable, and 120 to 300 ° C is particularly preferable. When the support is relatively weak against heat, the upper limit of the temperature is preferably 200 ° C. or lower, more preferably 150 ° C. or lower.

  A conductive pattern is formed on the surface of the printed matter obtained through the baking step by the metal contained in the conductive ink. Such a conductive pattern can be used for circuit boards, integrated circuit boards, and the like of various electric products.

  The conductive pattern was plated with a metal such as copper in order to form a highly reliable wiring pattern capable of maintaining good electrical conductivity without causing disconnection or the like over a long period of time. Things can be used. Specifically, as the conductive pattern, for example, a part of or the entire surface of the support has a receiving layer formed using the receiving layer forming resin composition, and the surface of the receiving layer is formed. A plating nucleus is supported on a part or all of the coating nucleus by applying a plating nucleus agent, and after passing through a baking step or the like as necessary, further after electrolytic plating treatment, electroless plating treatment, or after the electroless plating treatment What has a plating film formed by performing an electroplating process is mentioned.

  As the plating nucleating agent, one corresponding to the conductive ink exemplified as the fluid can be used. For example, a plating nucleus, specifically, a conductive material dispersed in a solvent is used. Can do.

  Examples of the conductive substance used for the plating nucleating agent include metal particles exemplified as the conductive substance usable for the conductive ink, oxides of the metal, and those whose surface is coated with an organic substance. One or more types can be used.

  The metal oxide is usually in an inactive (insulating) state, but it can be exposed to the metal and treated with a reducing agent such as dimethylaminoborane to impart activity (conductivity). It becomes.

  In addition, examples of the metal whose surface is coated with the organic substance include those in which a metal is contained in resin particles (organic substance) formed by an emulsion polymerization method or the like. These are usually in an inactive (insulating) state, but by removing the organic substance using, for example, a laser or the like, it becomes possible to expose the metal and impart activity (conductivity).

  The conductive substance contained in the plating nucleating agent preferably has an average particle diameter in the range of about 10 nm to 1 μm.

  Moreover, as a solvent used for the said plating nucleating agent, the thing similar to what was illustrated as solvents, such as an aqueous medium and an organic solvent which can be used for the said conductive ink, can be used.

  In the electroless plating treatment step, for example, a metal such as copper contained in the electroless plating solution by bringing the electroless plating solution into contact with the surface of a receiving substrate on which a plating nucleus such as palladium or silver is supported. In which an electroless plating film made of a metal film is formed.

  As the electroless plating solution, for example, a material containing a conductive material made of a metal such as copper, nickel, chromium, cobalt, tin, a reducing agent, and a solvent such as an aqueous medium or an organic solvent may be used. it can.

  Examples of the reducing agent that can be used include dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, and phenols.

  In addition, as the electroless plating solution, if necessary, monocarboxylic acids such as acetic acid and formic acid; dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid; malic acid, lactic acid, glycolic acid Hydroxycarboxylic acids such as gluconic acid and citric acid; amino acids such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid and glutamic acid; aminopoly acids such as iminodiacetic acid, nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid It may contain complexing agents such as organic acids such as carboxylic acids, soluble salts of these organic acids (sodium salts, potassium salts, ammonium salts, etc.), amines such as ethylenediamine, diethylenetriamine, and triethylenetetramine. .

  The temperature of the electroless plating solution when the electroless plating solution is brought into contact with the surface of the receiving substrate on which the plating nucleus in the plating nucleating agent is supported is generally in the range of 20 ° C to 98 ° C. preferable.

  In addition, the electrolytic plating treatment step may be performed by applying an electrolytic plating solution to the surface (x) of the receiving substrate on which the plating nucleus is supported or the surface (y) of the electroless plating film formed by the electroless treatment, for example. By energizing in the state of contact, a metal such as copper contained in the electrolytic plating solution can be used for the surface (x) of the receiving base placed on the negative electrode or the electroless plating film formed by the electroless treatment. It is a step of depositing on the surface (y) to form an electrolytic plating film (metal film).

  As said electroplating liquid, what contains the electroconductive substance which consists of metals, such as copper, nickel, chromium, cobalt, tin, a sulfuric acid, etc., and an aqueous medium can be used.

  The temperature of the electrolytic plating solution when the electrolytic plating solution is brought into contact with the surface of the receiving substrate on which the plating nucleus in the plating nucleating agent is supported is preferably in the range of about 20 ° C to 98 ° C.

  In the electroless plating process and the electroplating process as described above, a strong acid or strong alkaline plating solution as described above is often used. It often causes peeling of the receiving layer from the support.

  On the other hand, after printing on the receiving substrate of the present invention using a fluid such as a plating nucleating agent, the receptor layer is peeled off from the support in the plating treatment step for the cross-linked structure formed in the receiving layer. Will not cause. In particular, even if the support is made of a polyimide resin or the like, it does not cause peeling of the receiving layer, and therefore can be used very suitably for the production of the conductive pattern.

  The conductive pattern as described above is, for example, the formation of an electronic circuit using silver ink or the like, an organic solar cell or an electronic book terminal, an organic EL, an organic transistor, a flexible printed circuit board, an RFID, etc. It can be suitably used for forming and forming a conductive pattern, more specifically, a circuit board in manufacturing an electromagnetic wave shield wiring of a plasma display.

  In addition, among the conductive patterns obtained by the above method, after printing using a fluid such as conductive ink or plating nucleating agent, the conductive pattern obtained by forming a crosslinked structure in the receiving layer, Silver ink, etc., because it can provide excellent durability at a level that can maintain good electrical conductivity without causing peeling of the receptor layer from the support, etc., even after undergoing a plating process Formation of circuit forming substrates used for electronic circuits and integrated circuits using organic solar cells, electronic book terminals, organic EL, organic transistors, flexible printed circuit boards, formation of RFID and other layers and peripheral wiring, Of the wiring for the electromagnetic wave shield of the plasma display, etc., it can be suitably used particularly for applications requiring durability. In particular, since the conductive pattern subjected to the plating treatment can form a highly reliable wiring pattern capable of maintaining good electrical conductivity without causing disconnection or the like over a long period of time, for example, a copper-clad laminate is generally used. (CCL: Copper Clad Laminate) and can be used for applications such as flexible printed circuit board (FPC), automatic tape bonding (TAB), chip-on-film (COF), and printed wiring board (PWB).

  Hereinafter, the present invention will be described in detail by way of examples.

[Reference Example 1] Production of Urethane Resin (A) -1 Polyester polyol (1,4-cyclohexanedimethanol and neopentylglycol in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer. Polyester polyol obtained by reacting with adipic acid, aliphatic cyclic structure content in the polyester polyol is 1426 mmol / kg, hydroxyl group equivalent 1000 g / equivalent) is 100 parts by mass, 2,2-dimethylolpropionic acid 17 .6 parts by mass, 1,4-cyclohexanedimethanol 21.7 parts by mass, dicyclohexylmethane diisocyanate 106.2 parts by mass in a mixed solvent of methyl ethyl ketone 178 parts by mass, urethane having an isocyanate group at the molecular terminal An organic solvent solution of the prepolymer was obtained.

  Next, 13.3 parts by mass of triethylamine is added to the organic solvent solution of the urethane resin to neutralize part or all of the carboxyl groups of the urethane resin, and 380 parts by mass of water is further added and sufficiently stirred. Thus, an aqueous dispersion of a urethane resin having an aliphatic cyclic structure and a carboxyl group was obtained.

  Next, 8.8 parts by mass of a 25% by mass ethylenediamine aqueous solution is added to the aqueous dispersion, and the particulate polyurethane resin is chain-extended by stirring, followed by aging / desolving, thereby solid content concentration 30 An aqueous dispersion of mass% urethane resin (A) -1 was obtained. The urethane resin (A) -1 obtained here had an acid value of 30, an aliphatic cyclic structure content calculated from the raw material ratio of 4452 mmol / kg, and a weight average molecular weight of 53,000.

[Reference Example 2] Production of Urethane Resin (A) -2 In a nitrogen-substituted container equipped with a thermometer, nitrogen gas introduction tube, and stirrer, 100 parts by mass of polyester polyol (neopentyl glycol and 1,6-hexane) Polyester polyol obtained by reacting diol and adipic acid, hydroxyl group equivalent 1000 g / equivalent),
By reacting 12.6 parts by mass of 2,2-dimethylolpropionic acid, 5.5 parts by mass of 1,4-cyclohexanedimethanol, and 58.2 parts by mass of dicyclohexylmethane diisocyanate in a mixed solvent of 124 parts by mass of methyl ethyl ketone. An organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.

  Next, by adding 9.5 parts by mass of triethylamine to the organic solvent solution of the urethane resin, part or all of the carboxyl groups of the urethane resin is neutralized, and further 277 parts by mass of water is added and sufficiently stirred. An aqueous dispersion of urethane resin having an aliphatic cyclic structure and a carboxyl group was obtained.

  Next, 4.8 parts by mass of a 25% by mass ethylenediamine aqueous solution is added to the aqueous dispersion, and the particulate polyurethane resin is chain-extended by stirring, followed by aging and desolvation, whereby a solid content concentration of 30 is obtained. An aqueous dispersion of mass% urethane resin (a1) -2 was obtained. The urethane resin (A) -2 obtained here had an acid value of 30, an aliphatic cyclic structure content calculated from the raw material ratio of 2714 mmol / kg, and a weight average molecular weight of 51,000.

[Reference Example 3] Production of Urethane Resin (A) -3 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 100 parts by mass of polyester polyol (1,4-cyclohexanedimethanol and neo 18. Polyester polyol obtained by reacting pentyl glycol and adipic acid, aliphatic cyclic structure content in the polyester polyol: 1426 mmol / kg, hydroxyl group equivalent 1000 g / equivalent), 2,2-dimethylolpropionic acid 6 parts by mass, 1,4-cyclohexanedimethanol 21.7 parts by mass, dicyclohexylmethane diisocyanate 106.2 parts by mass in a mixed solvent with methyl ethyl ketone 178 parts by mass, urethane having an isocyanate group at the molecular terminal An organic solvent solution of the prepolymer was obtained.

  Next, 10 parts by mass of γ-aminopropyltriethoxysilane is mixed with the organic solvent solution of the urethane prepolymer, and the urethane prepolymer and γ-aminopropyltriethoxysilane are reacted to form an aliphatic cyclic structure. An organic solvent solution of a urethane resin having a carboxyl group and a hydrolyzable silyl group or silanol group was obtained.

  Next, 13.3 parts by mass of triethylamine is added to the organic solvent solution of the urethane resin to neutralize part or all of the carboxyl groups of the urethane resin, and 380 parts by mass of water is further added and sufficiently stirred. An aqueous dispersion of urethane resin was obtained.

  Next, 8.8 parts by mass of a 25% by mass ethylenediamine aqueous solution is added to the aqueous dispersion, and the particulate polyurethane resin is chain-extended by stirring, followed by aging / desolving, thereby solid content concentration 30 An aqueous dispersion of mass% urethane resin (a1) -3 was obtained. The urethane resin (a1) -3 obtained here had an acid value of 30, an aliphatic cyclic structure content calculated from the charged raw material ratio of 4307 mmol / kg, and a weight average molecular weight of 88,000.

Reference Example 4 Production of Urethane Resin (A) -4 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 100 parts by mass of polyether polyol (“PTMG2000” manufactured by Mitsubishi Chemical Corporation) , Hydroxyl group equivalent 1000 g / equivalent), 2,2-dimethylolpropionic acid 17.4 parts by mass, 1,4-cyclohexanedimethanol 34.2 parts by mass, dicyclohexylmethane diisocyanate 109.3 parts by mass, isophorone diisocyanate 31.5 By reacting parts by mass in a mixed solvent of 178 parts by mass of methyl ethyl ketone, an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.

  Next, 12.5 parts by mass of γ-aminopropyltriethoxysilane is mixed with the organic solvent solution of the urethane prepolymer, and the urethane prepolymer and γ-aminopropyltriethoxysilane are reacted to form an aliphatic ring. An organic solvent solution of a urethane resin having a formula structure, a carboxyl group, and a hydrolyzable silyl group or silanol group was obtained.

  Next, 13.1 parts by mass of triethylamine is added to the organic solvent solution of the urethane resin to neutralize part or all of the carboxyl groups of the urethane resin, and 488 parts by mass of water is further added and sufficiently stirred. An aqueous dispersion of urethane resin was obtained.

  Next, 17 parts by mass of a 25% by mass aqueous ethylenediamine solution is added to the aqueous dispersion, and the resulting polyurethane resin is chain-extended by stirring, followed by aging and desolvation, thereby solid content concentration of 30% by mass. An aqueous dispersion of urethane resin (A) -4 was obtained. The urethane resin (A) -4 obtained here had an acid value of 25, an aliphatic cyclic structure content calculated from the raw material ratio of 3921 mmol / kg, and a weight average molecular weight of 99000.

[Reference Example 5] Production of Urethane Resin (A) -5 Polycarbonate polyol (1,4-cyclohexanedimethanol and carbonate ester was added in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer. A polycarbonate diol containing an aliphatic cyclic structure obtained by reaction, an aliphatic cyclic structure content in the polycarbonate polyol of 3000 mmol / kg, a hydroxyl group equivalent of 1000 g / equivalent) is 100 parts by mass, and 2,2-dimethylol By reacting 9.7 parts by mass of propionic acid, 5.5 parts by mass of 1,4-cyclohexanedimethanol, and 51.4 parts by mass of dicyclohexylmethane diisocyanate in a mixed solvent of 111 parts by mass of methyl ethyl ketone, an isocyanate group is formed at the molecular terminal. Obtained an organic solvent solution of urethane prepolymer having .

  Next, 7.3 parts by mass of triethylamine is added to the organic solvent solution of the urethane resin to neutralize part or all of the carboxyl groups of the urethane resin, and 355 parts by mass of water is further added and sufficiently stirred. Thus, an aqueous dispersion of a urethane resin having an aliphatic cyclic structure and a carboxyl group was obtained.

  Next, 4.3 parts by mass of a 25% by mass ethylenediamine aqueous solution is added to the aqueous dispersion, and the particulate polyurethane resin is chain-extended by stirring, followed by aging / desolving, so that the solid content concentration is 30. An aqueous dispersion of mass% urethane resin (A) -5 was obtained. The urethane resin (A) -5 obtained here had an acid value of 24, an aliphatic cyclic structure content calculated from the raw material ratio of 4356 mmol / kg, and a weight average molecular weight of 61,000.

[Reference Example 6] Production of Urethane Resin (A) '-1 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 100 parts by mass of polyether polyol ("PTMG2000" Mitsubishi Chemical Corporation) Manufactured in a mixed solvent of 118 parts by mass of methyl ethyl ketone, 7.9 parts by mass of 2,2-dimethylolpropionic acid, 3.0 parts by mass of neopentyl glycol, and 41.0 parts by mass of isophorone diisocyanate. By making it react, the organic solvent solution of the urethane prepolymer which has an isocyanate group in the molecular terminal was obtained.

Next, 4.2 parts by mass of 3-aminopropyltriethoxysilane is mixed with the organic solvent solution of the urethane prepolymer, and the urethane prepolymer and 3-aminopropyltriethoxysilane are reacted to cause hydrolysis. An organic solvent solution of a urethane resin having a silyl group or silanol group and a hydrophilic group was obtained.
Next, 5.9 parts by mass of triethylamine is added to the organic solvent solution of the urethane resin to neutralize part or all of the carboxyl groups of the urethane resin, and further, 230 parts by mass of water is added and sufficiently stirred. An aqueous dispersion of urethane resin was obtained.

  Next, 5.6 parts by mass of a 25% by mass ethylenediamine aqueous solution is added to the aqueous dispersion, and the resulting polyurethane resin is chain-extended by stirring, followed by aging and desolvation, thereby solid content concentration 30 An aqueous dispersion of mass% urethane resin (A) ′-1 was obtained. The urethane resin (A) ′-1 obtained here had an acid value of 22, an aliphatic cyclic structure content calculated from the raw material ratio of 1172 mmol / kg, and a weight average molecular weight of 97,000.

[Reference Example 7] Production of Urethane Resin (A) '-2 Polyester polyol (1,4-cyclohexanedimethanol and neopentyl glycol) in a nitrogen-substituted container equipped with a thermometer, nitrogen gas inlet tube, and stirrer Polyol obtained by reacting adipic acid with adipic acid, the aliphatic cyclic structure content in the polyester polyol is 1425 mmol / kg, and the hydroxyl equivalent is 1000 g / equivalent) 100 parts by mass, 2,2-dimethylolpropion By reacting 49.7 parts by mass of acid, 127.1 parts by mass of 1,4-cyclohexanedimethanol and 416.8 parts by mass of dicyclohexylmethane diisocyanate in a mixed solvent of 492 parts by mass of methyl ethyl ketone, an isocyanate group is formed at the molecular terminal. Obtained organic solvent solution of urethane prepolymer having

  Next, 37.5 parts by mass of triethylamine is added to the organic solvent solution of the urethane resin to neutralize part or all of the carboxyl groups of the urethane resin, and 1083 parts by mass of water is further added and sufficiently stirred. Thus, an aqueous dispersion of a urethane resin having an aliphatic cyclic structure and a carboxyl group was obtained.

  Next, 34.4 parts by mass of a 25% by mass ethylenediamine aqueous solution is added to the aqueous dispersion and stirred to chain-extend the particulate polyurethane resin, and then aged and desolventized to obtain a solid content concentration of 30. An aqueous dispersion of mass% urethane resin (A) ′-2 was obtained. The urethane resin (A) ′-2 obtained here had an acid value of 30, an aliphatic cyclic structure content calculated from the ratio of charged raw materials, 5984 mmol / kg, and a weight average molecular weight of 70000.

[Reference Example 8] Production of vinyl polymer (B) -1 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, and a dropping funnel, 115 parts by mass of deionized water, Latemul E-118B (Kao) 4 parts by mass were added and heated to 75 ° C. while blowing nitrogen.

  Under stirring, a vinyl monomer mixture comprising 60.0 parts by mass of methyl methacrylate, 38.0 parts by mass of n-butyl acrylate, and 2.0 parts by mass of methacrylic acid in a reaction vessel, and Aqualon KH-1025 ( Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient 25% by mass) Add a part (5 parts by mass) of the monomer pre-emulsion obtained by mixing 4 parts by mass and 15 parts by mass of deionized water. 0.1 parts by mass of potassium sulfate was added, and polymerization was performed for 60 minutes while maintaining the temperature in the reaction vessel at 75 ° C.

  Next, while maintaining the temperature in the reaction vessel at 75 ° C., the remaining monomer pre-emulsion (114 parts by mass) and 30 parts by mass of an aqueous solution of potassium persulfate (active ingredient 1.0% by mass) were added dropwise to each other. It was added dropwise over 180 minutes using a funnel. After completion of dropping, the mixture was stirred at the same temperature for 60 minutes.

  The temperature in the reaction vessel was cooled to 40 ° C., and aqueous ammonia (10% by mass of active ingredient) was used so that the pH of the aqueous dispersion in the reaction vessel was 8.5.

  Next, deionized water was used so that the non-volatile content was 20.0% by mass, followed by filtration with a 200 mesh filter cloth to obtain an aqueous dispersion of vinyl polymer (B) -1.

Example 1 <Preparation of Receptive Layer Forming Resin Composition (I-1) and Production of Receptive Base Material (II-1) Using It>
The aqueous dispersion of urethane resin (A) -1 obtained above and the aqueous dispersion of -1 of vinyl polymer (B) were combined with the aqueous dispersion of urethane resin (A) -1: vinyl polymer (B-1 ) Water dispersion = 100: 350 (solid content mass ratio 30:70), and after using deionized water so that the non-volatile content is 20% by mass, by filtering through a 200 mesh filter cloth, A receptor layer-forming resin composition (I-1) used in the present invention was obtained.

  Using the bar coater, the resin composition for forming a receiving layer (I-1) was applied to the surfaces of three types of supports shown in the following (i) to (iii) so that the dry film thickness was 3 μm. It was coated and dried at 70 ° C. for 3 minutes using a hot air dryer to obtain three types of receiving substrates (II-1) having receiving layers formed on each support.

[Support]
(I) PET; polyethylene terephthalate film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd., thickness 50 μm)
(Ii) PI: Polyimide film (Kapton 200H manufactured by Toray DuPont Co., Ltd., thickness 50 μm)
(Iii) GL; glass: glass plate, JIS R3202, thickness 2 mm

Example 2 <Preparation of Receptor Layer Forming Resin Composition (I-2) and Production of Receptive Substrate (II-2) Using It>
A reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, dropping funnel for dropping the monomer mixture, dropping funnel for dropping the polymerization catalyst, 140 parts by mass of deionized water, urethane resin (A) obtained above -1 was added to 100 parts by mass, and the temperature was raised to 80 ° C. while blowing nitrogen.

  60.0 parts by mass of methyl methacrylate and 40.0 parts by mass of n-butyl acrylate to obtain the vinyl polymer (B) -2 constituting the core layer with stirring in a reaction vessel heated to 80 ° C. A monomer mixture consisting of 20 parts by mass of an aqueous ammonium persulfate solution (concentration: 0.5% by mass) was dropped from a separate dropping funnel over 120 minutes while maintaining the temperature in the reaction vessel at 80 ± 2 ° C. for polymerization. .

  After completion of dropping, the composite resin particles are constituted by a shell layer made of the urethane resin (A) -1 and a core layer made of the vinyl polymer (B) -2 by stirring at the same temperature for 60 minutes. An aqueous dispersion of (C) -1 was obtained.

  The reaction vessel is cooled to 40 ° C., then deionized water is used so that the non-volatile content becomes 20.0% by mass, and then filtered through a 200 mesh filter cloth. A resin composition for forming a receiving layer (I-2) was obtained.

  A bar coater was applied to the surface of three types of supports shown in the following (i) to (iii) so that the resin composition for forming a receiving layer (I-2) obtained above was 3 μm in dry film thickness. Each was coated using a hot air dryer and dried at 70 ° C. for 3 minutes using a hot air drier to obtain three types of receiving substrates (II-2) each having a receiving layer formed on each support.

Examples 3 to 5 <Preparation of Receptive Layer Forming Resin Compositions (I-3) to (I-5) and Production of Receiving Substrates (II-3) to (II-5) Using them>
The type of the urethane resin is changed to (A) -1 to (A) -3 described in Table 1 below, and the composition of the vinyl monomer used for the production of the vinyl polymer is described in Table 1 below. Resin compositions for forming a receiving layer (I-3) to (I-5) having a nonvolatile content of 20% by mass were prepared in the same manner as described in Example 2, except that each was changed.

  Three types of supports shown in the following (i) to (iii) are prepared from the resin compositions (I-3) to (I-5) for receiving layer formation obtained above so that the dry film thickness is 3 μm. The surface of each substrate was coated with a bar coater and dried at 70 ° C. for 3 minutes using a hot air drier to obtain three types of receiving substrates (II) having an ink receiving layer formed on each support. -3) to (II-5) were obtained.

  Example 6 <Preparation of Receptor Layer Forming Resin Composition (I-6) and Production of Receptive Substrate (II-6) Using It>

  200 parts by mass of the resin composition for receiving layer formation (I-2) obtained above, 3.0 parts by mass of a melamine compound [Beccamin M-3 (manufactured by DIC Corporation)], and deionized water are mixed. As a result, a resin composition (I-6) for forming a conductive receiving layer having a nonvolatile content of 20% by mass was obtained.

  A bar coater was applied to the surface of the three types of supports shown in (i) to (iii) below so that the resin composition for forming a receiving layer (I-6) obtained above was 3 μm in dry film thickness. Each was coated using a hot air dryer and dried at 70 ° C. for 3 minutes using a hot air dryer to obtain three types of ink receiving substrates (II-6) each having a receiving layer formed on each support. .

Examples 7 to 11 <Preparation of Receptive Layer Forming Resin Compositions (I-7) to (I-11) and Production of Ink Receiving Substrates (II-7) to (II-11) Using the Same>
The type of the urethane resin is changed to (A) -1 to (A) -5 described in Table 1 below, and the composition of the vinyl monomer used for the production of the vinyl polymer is described in Tables 1 and 2 below. Resin compositions for forming a receiving layer (I-7) to (I-11) having a nonvolatile content of 20% by mass were prepared in the same manner as in Example 2, except that the composition was changed to the composition.

  Three types of supports shown in the following (i) to (iii) are prepared from the resin compositions (I-7) to (I-11) for forming the receiving layer obtained above so that the dry film thickness becomes 3 μm. Each of the substrates was coated with a bar coater and dried at 70 ° C. for 3 minutes using a hot air drier to obtain three types of receiving substrates (II−) each having a receiving layer formed on each support. 7) to (II-11) were obtained.

Comparative Examples 1 and 2 <Preparation of Receptor Layer Forming Resin Compositions (I′-1) to (I′-2) and Receiving Substrates (II′-1) to (II′-2) Using them Production>
The type of the urethane resin is changed to (A) ′-1 to (A) ′-2 described in Table 1 below, and the composition of the vinyl monomer used for the production of the vinyl polymer is described in Table 2 below. Resin compositions for forming a receiving layer (I′-1) to (I′-2) having a nonvolatile content of 20% by mass were prepared in the same manner as described in Example 2 except that the composition was changed to the composition. .

  The three types of resin compositions (I′-1) to (I′-2) obtained as described above are represented by the following (i) to (iii) so that the dry film thickness is 3 μm. Three types of receiving substrates (each having a receiving layer formed on each support) were coated on the surface of the support using a bar coater and dried at 70 ° C. for 3 minutes using a hot air dryer. I'-1) to (I'-2) were obtained.

Comparative Example 3 <Preparation of Receptive Layer Forming Resin Composition and Production of Receiving Substrate (II′-3) Using the Same>
The aqueous dispersion of urethane resin (A) -1 obtained above was used as a resin composition for forming a receiving layer (I′-3).

  Using the bar coater on the surface of the three types of supports shown in the following (i) to (iii), the resin composition for forming the receiving layer (I′-3) is dried to a thickness of 3 μm. Each was coated and dried at 70 ° C. for 3 minutes using a hot air drier to obtain three types of receiving substrates (II′-3) having an ink receiving layer formed on each support.

Explanation of Abbreviations in Tables 1 and 2 MMA: Methyl methacrylate BA: n-butyl acrylate NBMAM: Nn-butoxymethylacrylamide HEMA; 2-hydroxyethyl methacrylate 4HBA; 4-hydroxybutyl acrylate MAA: methacrylic acid cross-linking Agent 1: Melamine compound (DIC Corporation Becamine M-3, Trimethoxymethyl Melamine)

[Method for specifying content of aliphatic cyclic structure]
The total mass of all raw materials such as polyol and polyisocyanate used in the production of the urethane resin and the compound having an aliphatic cyclic structure used in the production of the urethane resin (a polyol or an aliphatic ring having an aliphatic cyclic structure) Calculation was based on the amount of the aliphatic cyclic structure possessed by the polyisocyanate having the formula structure.

[Method for evaluating adhesion between support and receiving layer]
A cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) is pressure-bonded to the surface (on the receiving layer) of each receiving substrate before printing, and then the cellophane adhesive tape is attached to the receiving substrate. Peeling in the direction of 90 degrees with respect to the surface. The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.

  The adhesive layer of the peeled cellophane adhesive tape was “A” in which no receptor layer was attached, and the receptor layer in a range of less than about 5% relative to the adhesive tape application area was peeled from the support, The adhesive layer attached to the adhesive tape is "B". The adhesive layer in the range of about 5% to less than 50% of the adhesive tape is peeled off from the support, and the adhesive layer attached to the adhesive tape is "C". About 50% or more of the receiving layer with respect to the affixing area was peeled off from the support and was attached to the adhesive tape as “D”.

[Method for evaluating printability]
An ink jet printer (SP-300V manufactured by Roland Co., Ltd.) was applied to the surface of the receiving substrate obtained using “(i) PET; polyethylene terephthalate film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd., thickness 50 μm)” as a support. ), And the following nine solvent-based pigment inks containing a glycol-based high-polarity solvent and a pigment as a fluid are overlaid and printed in the order illustrated below to obtain a printed image of 100% to 400% solid image Obtained.

[Description of 9 color inks]
・ C100% ink ・ Y100% ink ・ M100% ink ・ Bk100% ink ・ Total 200% ink composed of C100% and M100% ・ Total 200% ink composed of M100% and Y100% ・ Y100% and C100% 200% ink consisting of C100%, M100% and Y100% total 300% ink C100%, M100% Y100% and K100% total 400% ink

  The printability of a printed image obtained by printing using the solvent-based pigment ink was evaluated based on the following criteria.

  A: A uniform print image was formed with no color unevenness, bleeding, cracks, etc. occurring in the print image formed using the “400% ink in total”.

  B: The printed image formed using the “300% total ink” had no color unevenness, bleeding, cracks, etc., but was subsequently superimposed on the printed image, The printed image obtained by printing with “400% ink” showed slight blurring and color unevenness.

  C: “200% total ink consisting of C100% and M100%”, “200% total ink consisting of M100% and Y100%”, and “200% total consisting of Y100% and C100%” The print image formed by printing using “ink” did not show any color unevenness, blurring, cracks, etc., but was subsequently superimposed on the print image, and the “total of 300% ink” was added. The printed image obtained by printing using the image had blurring and color unevenness.

  D: Printed images formed using the “C100% ink”, “Y100% ink”, “M100% ink”, and “Bk100% ink” had no color unevenness, blurring, or cracks. However, the print image obtained by successively superimposing on the print image and printing using the “total of 200% of ink” showed blurring and color unevenness.

  E: Bleeding, color unevenness, and cracks occur in the obtained printed image when printing is performed using any of the inks “C100% ink”, “Y100% ink”, “M100% ink”, and “Bk100% ink”. It was observed.

  [Method for preparing conductive ink as fluid]

[Ink preparation method]
[Preparation of nano silver ink 1 for inkjet printing]
Silver particles having an average particle diameter of 30 nm are dispersed in a mixed solvent composed of 65 parts by mass of diethylene glycol diethyl ether, 18 parts by mass of γ-butyrolactone, 15 parts by mass of tetraethylene glycol dimethyl ether, and 2 parts by mass of tetraethylene glycol monobutyl ether. Thus, a nano-silver ink 1 for solvent-based inkjet printing was prepared.

[Preparation of nano silver ink 2 for inkjet printing]
Nano silver ink 2 for solvent-based inkjet printing was prepared by dispersing silver particles having an average particle size of 30 nm in a solvent made of tetradodecane.

[Preparation of silver paste for screen printing]
A silver paste (NPS manufactured by Harima Chemicals Co., Ltd.) was used.

[Printing by inkjet printing method]
Inkjet printers (Konica Minolta IJ Co., Ltd.) were applied to the surfaces of three types of receiving substrates obtained by using the supports (i), (ii) and (iii), respectively. By using a company inkjet tester EB100, evaluation printer head KM512L, discharge amount 42 pl), printing a straight line having a line width of 100 μm and a film thickness of 0.5 μm by about 1 cm, and then drying at 150 ° C. for 30 minutes. , Printed matter (conductive pattern) was obtained. When the receiving substrates described in Examples 4 to 6 and 8 to 11 were used, the printing was performed using the conductive ink, and then the receiving substrate was subjected to a drying process at 150 ° C. for 30 minutes. A cross-linked structure was formed in the layer. As shown in Tables 3 and 4, whether or not the crosslinked structure was formed was determined by “gel fraction of the conductive ink receiving layer formed by drying at room temperature (23 ° C.) and then heating at 70 ° C. And “the gel fraction of the conductive ink receiving layer formed by further heating at 150 ° C.”. That is, the gel fraction of the conductive ink receiving layer obtained by heating at 150 ° C. is compared with the gel fraction (uncrosslinked state) of the conductive ink receiving layer obtained by drying at room temperature and then heating at 70 ° C. Then, it was judged that the cross-linked structure was formed by heating at a high temperature when the amount increased by 25% by mass or more.

  The gel fraction of the receptor layer formed by drying at room temperature (23 ° C.) and then heating at 70 ° C. was calculated by the following method.

  A resin composition for forming a receiving layer is poured onto a polypropylene film surrounded by cardboard so that the film thickness after drying becomes 100 μm, dried under conditions of a temperature of 23 ° C. and a humidity of 65% for 24 hours, and then 70 ° C. The receptor layer was formed by heat treatment for 3 minutes. The obtained receiving layer was peeled off from the polypropylene film and cut into a size of 3 cm in length and 3 cm in width to make a test piece. After measuring the mass (X) of the test piece 1, the test piece 1 was immersed in 50 ml of methyl ethyl ketone adjusted to 25 ° C. for 24 hours.

  By the immersion, the residue (insoluble matter) of the test piece 1 that did not dissolve in methyl ethyl ketone was filtered through a 300-mesh wire mesh.

  The mass (Y) of the residue obtained above was dried at 108 ° C. for 1 hour and measured.

  Subsequently, the gel fraction was calculated based on the formula of [(Y) / (X)] × 100 using the values of the masses (X) and (Y).

  The “gel fraction of the receiving layer formed by heating at 150 ° C.” was calculated by the following method.

  A resin composition for forming a receiving layer is poured onto a polypropylene film surrounded by cardboard so that the film thickness after drying is 100 μm, dried under conditions of a temperature of 23 ° C. and a humidity of 65% for 24 hours, and then 150 ° C. The receptor layer was formed by heating and drying for 30 minutes. The obtained receiving layer was peeled off from the polypropylene film and cut into a size of 3 cm in length and 3 cm in width to make a test piece 2. After measuring the mass (X ′) of the test piece 2, the test piece 2 was immersed in 50 ml of methyl ethyl ketone adjusted to 25 ° C. for 24 hours.

  By the immersion, the residue (insoluble matter) of the test piece 2 that did not dissolve in methyl ethyl ketone was filtered through a 300-mesh wire mesh.

  The mass (Y ′) of the residue obtained above was dried at 108 ° C. for 1 hour and measured.

  Next, using the mass (X ′) and (Y ′) values, the gel fraction was calculated based on the formula [(Y ′) / (X ′)] × 100.

[Printing by screen printing]
Using the screen plate of the metal mesh 250, the screen printing silver paste was applied to the surfaces of three kinds of receiving substrates obtained using the supports (i), (ii) and (iii), respectively. A straight line having a width of 50 μm and a film thickness of 1 μm was printed by about 1 cm, and then dried at 150 ° C. for 30 minutes to obtain a printed matter (conductive pattern).
About the receiving base material of Examples 4-6, 8-11, after printing using the said ink, a crosslinked structure is formed in an ink receiving layer by passing through a drying process for 30 minutes on the said 150 degreeC conditions. Been formed. The presence or absence of a crosslinked structure was determined by the same method as described above.

[Evaluation method of fine line]
The entire printed part (line part) formed on the surface of the printed matter (conductive pattern) obtained by the above-described method is observed using an optical microscope (Keyence Corporation digital microscope VHX-100), and the printed part The presence or absence of bleeding was confirmed.

  Specifically, no blur is observed at the outer edge of the printed part (line part), the boundary between the printed part and the non-printed part is clear, and there is a difference in height between the outer edge part and the central part of the line part. “A”, which is not seen, is smooth as the entire line part, and although slight blurring is confirmed in a very small part of the outer edge of the printed part (line part), the printed part and the non-printed part as a whole “B” indicates that the boundary is clear and the entire line portion is smooth, and a slight blur can be confirmed within a range of about 1/3 of the outer edge portion of the print portion (line portion). Although the boundary between the non-printing portion and the non-printing portion is partially unclear, the entire line portion is smooth and usable level is “C”, which is about 1/3 of the outer edge portion of the printing portion (line portion). Bleeding can be confirmed in a range of about ½, and the boundary between the printed part and the non-printed part becomes partially unclear at that part, and the outer edge part and the center of the line part "D" indicates that the image was not smooth, and bleeding can be confirmed in a range of about 1/2 or more of the outer edge of the printed part (line part), and the boundary between the printed part and the non-printed part is partially in that part. The result was unclear and was not smooth between the outer edge and the center of the line part, and was evaluated as “E”.

[Evaluation method of conductivity]
The nano silver ink 1 for inkjet printing was applied to the surface of two types of receiving substrates obtained using the supports (i) and (ii), respectively, and an inkjet printer (ink tester EB100 manufactured by Konica Minolta IJ Co., Ltd.). By using a printer head for evaluation KM512L and a discharge amount of 42 pl), a rectangular range (area) of 3 cm in length and 1 cm in width is printed with a film thickness of 0.5 μm and then dried at 150 ° C. for 30 minutes. , Printed matter (conductive pattern) was obtained. When the receiving substrates described in Examples 4 to 6 and 8 to 11 were used, the ink receiving layer was subjected to a drying process for 30 minutes at 150 ° C. after printing using the ink. A crosslinked structure was formed.

  In addition, the screen printing silver paste was formed on a surface of two types of receiving substrates obtained using the supports (i) and (ii), respectively, using a screen plate of a metal mesh 250, 3 cm in length, A 1 cm wide rectangular area (area) was printed at a film thickness of 1 μm, and then dried at 150 ° C. for 30 minutes to obtain a printed matter (conductive pattern).

The volume resistivity of the solid printed portion in the rectangular range of 3 cm in length and 1 cm in width formed on the surface of the printed matter (conductive pattern) obtained by the above-described method was measured using a Loresta pointer meter (MCP-T610 manufactured by Mitsubishi Chemical Corporation). It measured using. What volume resistivity is less than 5 × ^{10 -6} Ω · cm "A", 5 × ^{10 -6} or 9 × ^{10 -6} Ω · less than cm "B what is sufficient available levels "C", a level that is 9 × 10 ⁻⁶ or more and less than 5 × 10 ⁻⁵ Ω · cm and can be used, and “C”, that is 5 × 10 ⁻⁵ or more and less than 9 × 10 ⁻⁵ Ω · cm Was evaluated as “E”, which was 9 × 10 ⁻⁵ or more and difficult to use practically.

[Durability evaluation method after electroless plating]
Silver particles (plating nuclei) having an average particle diameter of 30 nm were mixed with a mixed solvent consisting of 65 parts by mass of diethylene glycol diethyl ether, 18 parts by mass of γ-butyrolactone, 15 parts by mass of tetraethylene glycol dimethyl ether and 2 parts by mass of tetraethylene glycol monobutyl ether. ) Was dispersed to prepare a solvent-based plating nucleating agent 1.

  An ink jet printer (Konica Minolta IJ Co., Ltd. Inkjet Testing Machine EB100, Evaluation Printer Head KM512L, Discharge Amount 42 pl) is applied to the surface of the receiving substrate obtained by using the support (ii). A printed product was obtained by printing a solid 5 cm long and 5 cm wide square area (area) with a film thickness of 0.5 μm and then drying at 150 ° C. for 30 minutes. About the receiving base material of Examples 4-6, Examples 8-11, after printing using the said plating nucleating agent 1, by passing through a drying process for 30 minutes on the said 150 degreeC conditions, a receiving layer A crosslinked structure was formed.

  An activator (A screen A220 manufactured by Okuno Pharmaceutical Co., Ltd.) is applied to the surface of the printed matter obtained above (the surface on which the plating nucleus is supported), and the plating nucleus is activated under the condition of 55 ° C. × 5 minutes. Processed.

  Next, an electroless copper plating agent (OPC-750 manufactured by Okuno Pharmaceutical Co., Ltd.) was applied to the surface subjected to the activation treatment, and an electroless copper plating treatment was performed at 20 ° C. for 20 minutes.

  Thereby, the electroconductive pattern X (plating structure X) in which the plating film which consists of copper was formed in the surface with which the said plating nucleus was carry | supported was obtained.

  A cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) is pressure-bonded to the plating film surface of the conductive pattern X (plating structure X) obtained above with a finger, and the cellophane adhesive tape is then electrically conductive. Peeling was performed in the direction of 90 degrees with respect to the surface of the pattern X (plating structure X). The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.

  “A” indicates that no adherent was observed on the adhesive surface of the peeled cellophane adhesive tape, and it is any of metal plating, silver, and receiving layer within a range of less than about 5% of the adhesive tape application area. Is peeled off from the support and adhered to the adhesive tape within a range of about 5% to less than 50% of the adhesive area of the “B” adhesive tape. "C" peels off the support and adheres to the adhesive tape, and the metal plating, silver, or receiving layer peels off from the support within a range of about 50% or more of the adhesive tape application area. The thing adhering to the tape was evaluated as "D".

[Durability evaluation method after electrolytic plating]
Silver particles (plating nuclei) having an average particle diameter of 30 nm were mixed with a mixed solvent consisting of 65 parts by mass of diethylene glycol diethyl ether, 18 parts by mass of γ-butyrolactone, 15 parts by mass of tetraethylene glycol dimethyl ether and 2 parts by mass of tetraethylene glycol monobutyl ether. ) Was dispersed to prepare a solvent-based plating nucleating agent 1.

  An ink jet printer (Konica Minolta IJ Co., Ltd. Inkjet Testing Machine EB100, Evaluation Printer Head KM512L, Discharge Amount 42 pl) is applied to the surface of the receiving substrate obtained by using the support (ii). A printed product was obtained by printing a solid 5 cm long and 5 cm wide square area (area) with a film thickness of 0.5 μm and then drying at 150 ° C. for 30 minutes. About the receiving base material of Examples 4-6, Examples 8-11, after printing using the said plating nucleating agent 1, by passing through a drying process for 30 minutes on the said 150 degreeC conditions, a receiving layer A crosslinked structure was formed.

  An activator (A screen A220 manufactured by Okuno Pharmaceutical Co., Ltd.) is applied to the surface of the printed matter obtained above (the surface on which the plating nucleus is supported), and the plating nucleus is activated under the condition of 55 ° C. × 5 minutes. Processed.

  Next, copper sulfate plating (Top Lucina 81SW manufactured by Okuno Seiyaku Kogyo Co., Ltd.) is applied to the activated surface, and electroplating is performed under the conditions of 25 ° C., 3 Amp, 90 minutes / dm 2, whereby the conductive A conductive pattern Y (plating structure Y) was obtained in which a plating film made of copper was laminated on the surface of the plating film made of copper of the conductive pattern X (plating structure X).

  A cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) is pressure-bonded to the plating film surface of the conductive pattern Y (plating structure Y) obtained above with a finger, and then the cellophane adhesive tape is made conductive. Peeling was performed in the direction of 90 degrees with respect to the surface of the pattern X (plating structure X). The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.

  “A” indicates that no adherent was observed on the adhesive surface of the peeled cellophane adhesive tape, and it is any of metal plating, silver, and receiving layer within a range of less than about 5% of the adhesive tape application area. Is peeled off from the support and adhered to the adhesive tape within a range of about 5% to less than 50% of the adhesive area of the “B” adhesive tape. "C" peels off the support and adheres to the adhesive tape, and the metal plating, silver, or receiving layer peels off from the support within a range of about 50% or more of the adhesive tape application area. The thing adhering to the tape was evaluated as "D". The case where the plating film was not peeled or the plating was not deposited during the plating treatment step was designated as “E”.

The receiving substrate obtained in Example 1 had excellent adhesion to the polyethylene terephthalate substrate and had good adhesion to both the polyimide substrate and the glass substrate. In addition, the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had excellent printability. Moreover, the electroconductive pattern provided with the outstanding thin wire property and favorable electroconductivity was able to be obtained by printing various nano silver ink on the said receiving base material.
The receiving substrate obtained in Example 2 had excellent adhesion to any of a polyethylene terephthalate substrate, a polyimide substrate, and a glass substrate. In addition, the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had excellent printability. In addition, by printing various nano silver inks on the receiving substrate, it was possible to obtain a conductive pattern that had excellent thin-line property and electrical conductivity and had durability that could withstand plating treatment.
In addition, the receiving substrate obtained in Example 3 had excellent adhesion to the polyethylene terephthalate substrate, and had good adhesion to both the polyimide substrate and the glass substrate. . Further, the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had good printability. In addition, by printing various types of nano silver ink on the receiving substrate, it is possible to obtain a conductive pattern having good thinness and electrical conductivity and durability enough to withstand plating treatment. It was.
Since the receiving base material obtained in Examples 4 and 5 has a component that forms a crosslinked structure, it has excellent adhesion to any of a polyethylene terephthalate base material, a polyimide base material, and a glass base material. there were. In addition, the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had excellent printability. In addition, by printing various nano silver inks on the receiving substrate, it was possible to obtain a conductive pattern that had excellent thin-line property and electrical conductivity and had durability that could withstand plating treatment.
The receiving base material obtained in Example 6 had excellent adhesion to any of a polyethylene terephthalate base material, a polyimide base material, and a glass base material since a crosslinking agent was used in combination. In addition, the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had excellent printability. In addition, by printing various types of nano silver ink on the receiving substrate, it is possible to obtain a conductive pattern having good thinness and electrical conductivity and durability enough to withstand plating treatment. It was.
The receiving base material obtained in Example 7 had excellent adhesion to any of a polyethylene terephthalate base material, a polyimide base material, and a glass base material since a crosslinking agent was used in combination. Further, the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had good printability. In addition, by printing various types of nano silver ink on the receiving substrate, it is possible to obtain a conductive pattern having good thinness and electrical conductivity and durability enough to withstand plating treatment. It was.
The receiving base materials obtained in Examples 8 and 9 had excellent adhesion to any of a polyethylene terephthalate base material, a polyimide base material, and a glass base material. Further, the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had good printability. In addition, by printing various types of nano silver ink on the receiving substrate, it is possible to obtain a conductive pattern having good thinness and electrical conductivity and durability enough to withstand plating treatment. It was.
The receiving substrate obtained in Example 10 had good adhesion to a polyethylene terephthalate substrate, a polyimide substrate and a glass substrate. In addition, the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had excellent printability. In addition, by printing various nano silver inks on the receiving substrate, it was possible to obtain a conductive pattern that had excellent thin-line property and electrical conductivity and had durability that could withstand plating treatment.

  The receiving substrate obtained in Example 11 had excellent adhesion to the polyethylene terephthalate substrate and had good adhesion to both the polyimide substrate and the glass substrate. Further, the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had good printability. In addition, by printing various types of nano silver ink on the receiving substrate, it is possible to obtain a conductive pattern having good thinness and electrical conductivity and durability enough to withstand plating treatment. It was.

  On the other hand, the receiving substrate obtained in Comparative Example 1 using a urethane resin having an aliphatic cyclic structure ratio of 2000 mmol / kg or less is a polyethylene terephthalate substrate, a polyimide substrate, and a glass substrate. It did not have practically sufficient adhesion. Further, the printed matter obtained by printing the solvent-based pigment ink on the receiving base material does not have sufficient printability such as causing bleeding. In addition, even when various nano silver inks are printed on the receiving substrate, it may cause blurring of the image line, so that it was not possible to obtain a conductive pattern having good fineness and electrical conductivity. .

  The receiving substrate obtained in Comparative Example 2 using a urethane resin having an aliphatic cyclic structure ratio exceeding 5500 mmol / kg is practically sufficient for any of a polyethylene terephthalate substrate, a polyimide substrate and a glass substrate. It did not have good adhesion. Further, the printed matter obtained by printing the solvent-based pigment ink on the receiving base material does not have sufficient printability such as causing bleeding. In addition, even when various nano silver inks are printed on the receiving substrate, it may cause blurring of the image line, so that it was not possible to obtain a conductive pattern having good fineness and electrical conductivity. .

  The receiving substrate obtained in Comparative Example 3 containing no vinyl polymer did not have practically sufficient adhesion to any of the polyethylene terephthalate substrate, polyimide substrate and glass substrate. Further, the printed matter obtained by printing the solvent-based pigment ink on the receiving base material does not have sufficient printability such as causing bleeding. In addition, even when various nano silver inks are printed on the receiving substrate, it may cause blurring of the image line, so that it was not possible to obtain a conductive pattern having good fineness and electrical conductivity. .

Claims (19)

A resin composition for forming a receiving layer containing a urethane resin (A), a vinyl polymer (B), and an aqueous medium (C), wherein the urethane resin (A) is a total amount of the urethane resin (A). Having a 2,000 mmol / kg to 5,500 mmol / kg aliphatic cyclic structure and a hydrophilic group, based on the above. Composite resin particles (D) in which the urethane resin (A) and the vinyl polymer (B) are composed of a shell layer that is the urethane resin (A) and a core layer that is the vinyl polymer (B). The resin composition for forming a receiving layer according to claim 1. The resin composition for forming a receiving layer according to claim 1, wherein the resin composition for forming a receiving layer forms a layer that receives a fluid containing a conductive substance or a pigment. The receiving layer according to claim 3, wherein the fluid containing the conductive substance or the pigment is a conductive ink containing a conductive substance, a plating nucleating agent containing a conductive substance, or a pigment ink containing a pigment. Resin composition for forming. The vinyl polymer (B) contains 10% by mass to 70% by mass of methyl methacrylate and 10% by mass to 50% by mass of (meth) acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms. The resin composition for forming a receiving layer according to claim 1, which is obtained by polymerizing a vinyl monomer mixture contained therein. The mass ratio [(A) / (B)] of the urethane resin (A) and the vinyl polymer (B) constituting the composite resin particle (D) is in the range of 70/30 to 10/90. The resin composition for forming a receiving layer according to claim 2. The resin composition for forming a receiving layer according to claim 1, wherein the vinyl resin (B) has a crosslinkable functional group. The resin composition for forming a receiving layer according to claim 7, wherein the crosslinkable functional group is one or more thermally crosslinkable functional groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group. Furthermore, it contains a crosslinking agent (E), Comprising: The said crosslinking agent (E) can perform a crosslinking reaction by heating to 100 degreeC or more, The receiving layer formation of Claim 1 or 7 Resin composition. The said crosslinking agent (E) is 1 or more types of thermal crosslinking agents (e1-2) chosen from the group which consists of a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and an isocyanate compound. A resin composition for forming a receiving layer. Urethane resin (A) having an aliphatic cyclic structure of 2,000 mmol / kg to 5,500 mmol / kg and a hydrophilic group, vinyl polymer (B), and a part or all of the support surface; It has a receiving layer formed using a resin composition for forming a receiving layer containing an aqueous medium (C), and the receiving layer is a receiving layer for receiving a fluid containing a conductive substance or a pigment. A receiving substrate, characterized in that it is. A printed matter printed on a receiving layer constituting the receiving substrate according to claim 11 by a fluid containing a conductive substance or a pigment. The printed matter according to claim 12, wherein the printing is performed by an inkjet printing method, a screen printing method, a letterpress reverse printing method, or a gravure offset printing method. Printing was performed on the receiving layer constituting the receiving substrate according to claim 11 by using a conductive ink containing a conductive substance or a fluid made of a plating nucleating agent containing a conductive substance. Conductive pattern. The receiving substrate according to claim 11, printed using a conductive ink containing a conductive substance or a fluid comprising a plating nucleating agent containing a conductive substance, and then the printed receiving layer. A conductive pattern obtained by forming a crosslinked structure on the substrate. The conductive pattern according to claim 14 or 15, wherein the conductive pattern is obtained by performing electrolytic plating or electroless plating treatment on a surface of a printed portion formed by printing the fluid. A conductive circuit comprising the conductive pattern according to claim 14. Urethane resin (A) having a 2,000 mmol / kg to 5,500 mmol / kg aliphatic cyclic structure and a hydrophilic group, vinyl polymer (B), and a part or all of the surface of the support, and And applying a resin composition for forming a receiving layer containing an aqueous medium (C), and drying the resin composition for forming a receiving layer under a condition that does not cause a crosslinking reaction. A printed matter comprising forming a receiving layer for receiving, then printing the fluid on the surface of the receiving layer, and then heating the printed receiving layer to form a crosslinked structure Manufacturing method. Urethane resin (A) having a 2,000 mmol / kg to 5,500 mmol / kg aliphatic cyclic structure and a hydrophilic group, vinyl polymer (B), and a part or all of the surface of the support, and In order to receive a fluid containing a conductive substance by applying a resin composition for forming a receiving layer containing an aqueous medium (C) and drying the resin composition for forming a receiving layer under a condition that does not undergo a crosslinking reaction. Then, the fluid is printed on the surface of the receptor layer to form a printed portion made of a conductive substance contained in the fluid, and then the printed receptor is formed. A method for producing a conductive pattern, comprising forming a crosslinked structure by heating a layer and then plating the printed portion formed on the surface of the receiving layer.